ZNOTES.

ORG

UPDATED TO 2022 SYLLABUS

CAIE A2 LEVEL
CHEMISTRY (9701)
SUMMARIZED NOTES ON THE SYLLABUS
CAIE A2 LEVEL CHEMISTRY (9701)

1.5. Born-Haber Cycle

1. Chemical Energetics ΔHfθ of an element under standard
conditions = 0
​

1.1. Enthalpy change of Atomization Endothermic Processes:

Bottom to top:
Enthalpy change of atomization
( ΔH θat ): enthalpy change
when 1 mole of gaseous atoms is formed from its
ΔHiθ ​

elements under standard conditions θ

ΔHat
e.g: Na (s) → Na (g)
​

e.g: 1/2Cl2 (g) → Cl (g) θ

ΔHea  2 nd  and 3 rd
​

Note: specific value may not be given and you must use
combination of enthalpies e.g. Exothermic Processes:
Top to bottom:

ΔHfθ ​

θ
ΔHea ​

θ
ΔHlatt ​

θ
ΔHhyd ​

1.2. Lattice Energy

Lattice Energy
( ΔH θlat ):
enthalpy change when one mole
of an ionic compound is formed from
its gaseous ions
under standard conditions.
e.g: Na+(g) + Cl-(g) → NaCl (s)
θ
More –ve ΔHlat ​
→ stronger ionic
bonding → more
stable ionic compound
θ
If theoretical and experimental
ΔHlat ​ value similar,
bonding is
pure ionic, otherwise it is intermediate
between ionic and covalent

1.3. Factors Affecting Lattice Energy 1.6. Dissolving Salts

θ Charge on Ion Enthalpy change of solution
( ΔH θsol ):
enthalpy change
ΔHlat ∝ ​

Radius of Ion when one mole of ionic solid is dissolved in

sufficient
​ ​

Radius of ion: the smaller the radius/smaller the size of water to form a very dilute solution under standard
ion, greater the charge density conditions (can be +ve or –ve)
Charge on ion: Greater charge density, greater e.g. NaCl(s) + aq → NaCl(aq)
electrostatic attraction between ions, ΔHlat
θ more
​
Enthalpy change of hydration
( ΔH θhyd ):
enthalpy change
​

exothermic, more stable compound when one mole of specified gaseous ions dissolves in
sufficient water to form a very dilute solution under
standard
conditions
1.4. ­Electron Affinity
e.g. Na+(g) + aq →
Na+(aq)
First electron Affinity ( ΔH θea ): enthalpy change when 1 Factors affecting Δ H θ hyd =
factors affecting Δ H θ lat
mole of electrons is added to 1 mole of gaseous atoms to Solubility of ionic salts depend on value of
ΔH θ sol : the
form 1 mole of gaseous anions under standard conditions more –ve = more
soluble
e.g: Cl (g) + e- → Cl- (g)
1st electron affinity is exothermic 1.7. Ion Polarization
2nd, 3rd… electron affinities are endothermic
because
when electron added to –ve ion, increased repulsion Ion polarization: distortion of the electron cloud on an
present
therefore requires input of energy anion
by a neighbouring cation

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Polarizing power: ability of a cation to attract electrons

and
distort and anion
Polarization will be increased by:
Cation has a higher charge density: high positive
charge and
small size
Anion has greater polarizability: high negative charge
and large
size

1.8. Thermal Stability of Gp.2 CO3 and

(NO3)2
Down the group, polarizing power decreases
‎
Mg 2+ > Ca2+ > Sr2+ >
Ba2+
The greater the polarization, the more distorted is the Electrolyte: compound that is decomposed (molten/ionic)
anion
causing it to weaken the C – O bond Electrodes: rods which allow current to enter electrolyte
Therefore, easier to form CO2 and XO and compound less (inert/reactive)
stable.
Order of stability: Ba2+ > Sr2+ >
Ca2+ > Mg 2+ 2.2. Product of Electrolysis

1.9. Solubility of Gp.2 Hydroxides & Molten Electrolyte:

Sulphates At the cathode: positive ions reduced to atoms

Radius of cation increases down group ∴ charge density Pb2+(l) + 2e- → Pb(s)
decreases
Attraction of cation to water molecule decreases ∴
value At the anode: negative ions oxidized to atoms/molecules

of ΔHhyd
θ becomes less
exothermic
2NO3-(l) → NO2(g) +
O2(g) + 2e-
​

ΔH θ lat also decreases but

decrease is relatively smaller
SO42-(l) → SO2(g) +
O2(g) + 2e-
because of large size of anions
compared to cations
ΔH θ sol becomes less exothermic
because decrease in Aqueous Electrolyte:
At the cathode At the anode
ΔH θ hyd is
greater than decrease in ΔH θ lat
∴ solubility of Hydroxide increase and Sulphate decrease E θ > 0‎then metal less E θ  > 0.4‎then non-metal
down the group By E θ reactive than H so metal less reactive than OH so
formed non-metal formed
E θ < 0‎then metal more E θ  < 0.4‎‎then non-metal
2. Electrochemistry reactive than H so H2(g) more reactive than OH so
​

 formed H2 O(l)  formed

​

2.1. Electrolysis By
Following results from
above, if solution very
Conc.
Electrolysis: decomposition of a compound into its dilute, this occurs greater:
element by an
electric current 4OH − ∗ (aq) →
2H + ∗ (aq) + 2e­−  →
2H2 O ∗ (l)  + O2(g)   +
  H ∗ 2(g)
​ ​

Electrolysis cell: 2eZ −

2.3. Quantitative Electrolysis

Calculating quantity of charge passed during electrolysis:

Q = It
in Coulombs (C)

Mass of a substance liberated is proportional to the

quantity of
electricity which passes through electrolyte
1 faraday (F): quantity of electric charge carried by 1 mol
of
electrons = 96,500 C

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CAIE A2 LEVEL CHEMISTRY (9701)

Relationship: F = Le
F = Faraday’s Constant
L = Avagadro’s Constant
e = charge on 1 electron
Example:
To liberate 1 mol of H2(g) ‎

Eθcell = EθRed - EθOx

2H+ ­-
(aq) + 2e → H2(g)
Eθcell ‎= 0.34 - -0.76 = 1.10‎
 ∴ requires 2 faradays of electricity to form 1 mole­
2.6. Salt Bridge
2.4. Standard Electrode Potentials
Used to complete the electrical circuit allowing the
Standard electrode (redox) potential
Eθ : the electrode movement of
ions between two half cells so that ionic
potential of a
half cell measured under standard balance is maintained;
electrically neutral
conditions using a standard
hydrogen electrode as the A strip of filter paper soaked in KNO3(aq)
other half cell Salt used should not react with ions forming a ppt. e.g. KCl
Standard cell potential
Eθcell : the
difference in standard in a
cell containing Ag 2+ would form insoluble ppt.
electrode potential between two half cells
Standard conditions: 2.7. Standard Hydrogen Electrode
Temperature: 298 K
Pressure: 1 atm (101 kPa) (S.H.E.)
Concentration: 1.00 mol dm-3
It is a reference cell, used to measure E θ of any other
half
cell
2.5. Electrochemical Cell Consists of H2(g) at 298K and 1atm bubbling around a Pt
electrode in contact with an aq. solution of H+ ions at
1.00
mol dm-3 conc. (e.g. HCl­(aq) or ½
H2SO4(aq))
Pt electrode is inert, allows conduction and is coated with
finely
divided Pt serving as a catalyst. Being porous,
retains large
amounts of H2(g)
‎
ANODE CATHODE
-ve electrode/half cell +ve electrode/half cell
Eθ of half-cell is more -ve (less Eθ of half-cell is more +ve
+ve) (less -ve)
Metal loses e-, forms +ve ions Metal ion gains e-, solid metal
= oxidation occurs deposited = reduction occurs
Cell Notation
‎
Zn(s) | Zn2+ (aq) Cu2+(aq) | Cu(s)
2.8. Measuring Eθ of a Half Cell using
S.H.E.
The more –ve (less +ve) the The more +ve (less -ve) the Metals in contact with their aq. solution
Eθ, the more easily it gets Eθ, the more easily it gets
oxidized ∴ stronger reducing reduced ‎∴‎stronger oxidizing
agent agent

Non-metals in contact with their aq. solution

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Fe3+ + e- ⇌
Fe2+­ E θ = 0.77V

If F e3+ increased or F e2+ decreased,

equi. favours
forward reaction ∴ E becomes more +ve
(0.85V)
If F e2+ increased or F e3+ decreased,
equi. favours
Pairs of ions with different oxidation states backward reaction ∴ E becomes more
-ve (0.70V)
A given reaction will occur under non-standard conditions
if the
E θ values of the two half reactions involved differ by
more than 0.30V
Changing conc. and non-standard conditions can also
cause
non-feasible standard reactions to occur as E
values can change
greatly

2.9. Feasibility of a Reaction 2.12. Nernst Equation

For a spontaneous (i.e. feasible) reaction,

Ecell
θ must be
​
Equation relating voltage of chemical cell to its standard
positive potential
and to concentrations of reactants & products

Finding whether a reaction is feasible:Will chlorine oxidize

RT [oxidized form ]
E = Eθ + ln  
F e2+  ions to Fe^{3+}$ ions? zF [reduced form]
​ ​

SolutionIdentify which is the R.A./O.A. from questionChlorine z is number of electrons transferred in reaction
is the O.A therefore is reducedIdentify relevant equations
F is the value of the Faraday constant 96,500 C
mol-1 
from data booklet and place in correct direction. If using
opposite direction, switch sign for value of Eθ Simplified relationship by substituting standard values
C l2 + 2e− → C l−
0.059 [oxidised form ]
​

E θ = +1.36 E = Eθ + log  
[reduced form]
​ ​

z
2+ 3+ −
Fe → Fe +e
θ
E = − (+0.77 ) If conc. less than 1 mol dm-3,
log [oxidized form] is –ve
and E is less
than E θ
Add Eθs together. If positive, reaction occurs and is feasible
otherwise, does not occur spontaneously. If conc. more than 1 mol dm-3,
log [oxidized form] is
+ve and E is more
than E θ
1.36 − 0.77 = 0.59
Reaction occurs spontaneously and is feasible
2.13. Hydrogen Fuel Cell
2.10. Oxidizing Ability of Halogens (Gp.
17)
Electrode potential values can be used to determine ease
of
oxidation or reduction
The more +ve E θ , the easier it is to reduce therefore
stronger oxidizing agent (ability).
Relative reactivity of halogens can be determined by Consists of:
ordering them
in descending order of E θ , most reactive Two platinum coated porous electrodes that allow
to least gases to pass
through
Electrolyte; either acidic or alkaline
Reaction Eθ
F2 + 2e-→ 2F- +2.87  
Acidic electrolyte:
Cl2 + 2e-→ 2Cl- +1.36
-ve Electrode (anode):
Br2 + 2e-→ 2Br- +1.07

I2 + 2e- → 2I- +0.54 2H2(g) 4H+(aq) + 4e-

+ve Electrode (cathode):

2.11. Concentration of aq. Ions

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O2(g) + 4H+(aq) + 4e-

2H2O(l) Strong Acids Weak Acids

Overall reaction: [H + ] [A− ]

Kc =
[HA] [H2 O]
​ ​

O2 + 2H2(g) 2H2O(l)
​

H+ ions removed at +ve electrode replaced by those Water dissociates very slightly; conc. remains constant ∴ can
produced at –ve electrode so conc. of electrolyte remains eliminate from equation
constant

[H + ] [A− ]
  Ka =
[HA]
​ ​

Alkaline electrolyte:

-ve Electrode (anode):

3.2. pH Scale
2H2(g) + 4OH-(aq)
4H2O(l) + 4e-
Gives strength of acid depending on
+ve Electrode (cathode):
H+
O2(g) + 2H2O(l) + 4e-
4OH-(aq)
Use – log  of values as they are very small giving pH
Overall reaction: Lower pH value, stronger the acid

O2 + 2H2(g) 2H2O(l) − log [H + ] = pH ⇔

[H + ] = 10 −pH
Calculating pH of a strong acid:
-
OH ions removed at -ve electrode replaced by those Find the pH of 3.6 × 10-5 mol dm-3
HNO3
produced at +ve electrode so conc. of electrolyte remains Solution
constant It is a strong acid and dissociates completely the conc. of ions
is
equal to conc. of the acid
 
Advantages: [H + ] = [HNO 3 ] = 3.6 × 10 −5
​

No pollutants – by product is water Calculate the pH by logging the conc.

More energy per gram of fuel than other fuels
Lightweight pH = − log (3.6 × 10 −5 ) = 4.44
Operate with high efficiency
3.3. Ionic Product of Water, Kw
3. Equilibria
Water molecules can function as both acids and bases;
one molecule
(base) accepts H+ from second one (acid)
3.1. Behaviour of Acids and Alkali
H2O(l) ⇌
H+(aq) + OH-(aq)
When acids and alkalis are added to water, they
dissociate/ionize and a dynamic equilibrium is set up [H + ] [OH− ]
General equilibrium of an acid (can be simplified to H+) Kc =
[H2 O]
​ ​

Strong Acids Weak Acids Conc. of water remains constant ∴ can eliminate from
HA(aq) + H2O(l) ‎→‎H+ + A- HA(aq) + H2O(l) ‎⇌‎H+ + A- equation and find the ionic product of water, Kw
(aq) (aq)
(aq) (aq)
Eq. position to the right Eq. position to the left
K w = [H + ] [OH− ]
​

Dissociates completely ‎∴‎ Dissociates partially ‎∴‎

At 25oC, the Kw of water is 1.00 x
10-14 mol2 dm-6
\[Acid\] = \[Ions\] \[Acid\] ‎≠‎\[Ions\]
− log throughout equation,
− log 1 × 10 −14 = 14 ∴

14 = pH + pOH

pH of an alkali can be calculated using this formula

 
Calculating pH of a strong base:

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CAIE A2 LEVEL CHEMISTRY (9701)

Calculate the pH of a solution of sodium hydroxide of [Salt]

pH = pK a + log ( )
concentration
0.05 mol dm-3 [Acid]
​ ​

Solution
Calculating pH of buffer solution:
It is a strong base and dissociates completely the conc. of
A buffer solution is made by adding 3.28g of CH3COONa to 1
ions is
equal to conc. of the solution
dm3 of 0.01 mol dm-3 CH3COOH
−
[OH ] = [NaOH] = 0.05
1. What is the pH of this buffer (Ka
= 1.8 ×  10 −5 )
Calculate pOH by logging
What is the change in pH when 1 cm3 of 1 mol
dm-3 NaOH is
pOH = − log 0.05 = 1.30
added to 1 dm3 of the buffer?
Calculate pH by using the following Solution
Part (a):
pH + pOH = 14 Calculate the moles and concentration of the salt
Moles
pH = 14 − pOH = 14 − 1.30 = 12.7
Mass 3.28
= = = 0.04
3.4. Buffer Solutions Molar Mass 82
​ ​

Concentration
Buffer solution: a solution in which pH doesn’t change
significantly when small amounts of acids or alkali added Moles 0.04
= = = 0.04
A buffer solution can be: Volume 1
​

Acid: Weak acid + its salt

Use formula to calculate pH:
e.g. CH3COH and CH3COONa
Alkali: Weak alkali + its salt 0.04
e.g. NH3 and NH4Cl pH = − log (1.8 × 10 −5 ) + log ( ) =5.35
0.01
​

In both types, the salt provides more of its conjugate pair,

for
example Part (b):
NaOH reacts with acid:
HA (aq) ⇌
H (aq) + A -(aq) &
MA (aq)
+
→ M (aq) +
A -(aq)
+
NaOH(aq) + CH3COOH(aq)
CH3COONa(aq) + H2O
Calculate no. of moles of NaOH used:
3.5. Working of an Acid Buffer Moles

= C oncentration ×  V olume = 1 ×  0.001 = 0.001

Hence that much of acid has been reduced and the same
amount has
formed as salt. Calculate new concentrations of
salt and acid.
Conc. of Acid

(0.01 × 1 )  – 0.001
3.6. Controlling pH of Blood = = 8.9 ×  10 −3
1  +  (1 ×  10 −3 )
​

Respiration in cells produces carbon dioxide and carbon Conc. of Salt

dioxide
combines with water in blood
0.04 +  0.001
= = 0.0410
H (aq) +
HCO3-(aq)
+ 1  +  (1 ×  10 −3 )
​

CO2(aq) + H2O(aq)
⇌

The enzyme carbonic anhydrase is present to supply Use formula to calculate pH:

HCO3- ions and increase its conc. similar to

acidic buffers 0.0410
pH = − log (1.8 × 10 −5 ) + log ( ) =5.40
8.99  ×  10 −3
​

If H+ increases: If H+ decreases:
Eq. shifts to the left Eq. shifts to the right Find the change in pH:

Reduces H+ Increases H+ ΔpH = 5.40 − 5.35 = 0.05

pH of blood unchanged
Calculating pH of buffer solution with different volumes of
acid and
salts:
3.7. Calculating pH of Buffer Solutions

( )

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CAIE A2 LEVEL CHEMISTRY (9701)

What is the pH of the buffer solution formed when 40cm3 of

1 K sp = [M g 2+ ][2F − ]2
​

mol dm-3 of nitrous acid (pKa = 3.34) is

added to 20 cm3 of 1 Solubility of salt = conc. of ions
mol dm-3 of sodium
hydroxide?
Solution ∴ [M g 2+ ] = [F − ] = 1.22 × 10 −3
Part (a):
Write out an equation for the reaction Substitute into equilibrium expression
K sp = (1.22 × ​

2
HNO2(aq) + NaOH(aq) NaNO2(aq) +
H2O(l) 10 −3 ) × 2 × (1.22 × 10 2 )
Calculate the moles of each reactant
K sp = 7.26 × 10 −9 mol3 dm−9
Moles of HNO2
​

To calculate solubility from solubility product, apply the

= 1 × (40 ×  10 −3 ) = 0.04 same
method but place x for conc. and find it
Moles of NaOH
3.9. Predicting Precipitation
= 1 × (20 ×  10 −3 ) = 0.02
Precipitation: when two aq. solutions of ionic substance
NaOH is limiting reagent therefore moles of product and
are
mixed, a ppt. will form provided the Ksp of the
reactants
are:
insoluble
solid is less than ionic product of ions present
NaNO2 formed $= 0.02$
HNO2 remaining $= 0.04 - 0.02 = 0.02$ Ionic Product > Ksp
Calculate concentration of salt and acid:  
Total Volume (20 + 40 ) × 10 −3 = 0.06
dm3 Predicting if insoluble salt will precipitate:
Conc. of HNO2= 0.02
0.06 = 3
​
1 ​
Will a ppt. BaCO3 (Ksp = 8.1 × 10 −9 )
form from solution
Conc. of NaNO2= 0.02 1
0.06 = 3
​ ​

containing 0.1 mol dm-3

Ba2+(aq) & 1.0 mol dm-3
CO32-(aq)
Use formula to calculate pH: Solution
1 Calculate ionic product:
pH = 3.34+ log ( 31 ) =3.34
​

0.1 × 1.0 = 1.0

​

3 ​

Compare to Ksp value

3.8. Solubility Product Ksp $1.0 > 8.1 \times 10^{- 9}\therefore$ ppt. will form

When a sparingly soluble salt is shaken with distilled

3.10. Common Ion Effect
water and
left to settle, the water contains aq. ions from
the salt in very
small conc. and a dynamic equilibrium is Common ion effect: lowering of solubility of an ionic
set up between ions and
insoluble solid compound
by addition of a common ion to the solution
Solubility product (Ksp): product of conc. of each
ion in a
saturated solution of sparingly soluble salt at 298K raised  
to the power of moles in dissociation equation e.g. Calculating solubility with common ion:
Fe2S 3(s) ⇌
2Fe3+(aq) + 3S 2-(aq) BaSO4 is a sparingly soluble salt (Ksp
= 1.0 × 10 −10 mol2
Ksp =
2Fe3+23S 2-3
units: mol5 dm-15 dm-6). Compare the
solubility at 298K of BaSO4 in an aq.
The conc. of ions is independent of amount of solid solution of 0.1 mol
dm-3 H2SO4 to in pure water
Ksp values change only with temperature Solution
Concentration of ions = solubility of salt
Calculate conc. of Ba2+ in pure water
Calculating solubility product from solubility: Ksp = $\lbrack Ba^{2+}\rbrack \lbrack So_4^{2-} \rbrack$ and
A saturated solution of magnesium fluoride, MgF2, has a both conc. are equal $\therefore$
solubility of 1.22 × 10 −3 mol dm-3. Calculate the
solubility
[Ba2+ ] = 1.0 × 10 −10 = 1.0 × 10 −5
product of magnesium fluoride.
​

Solution
To calculate$Ba2+, first find conc. of common ion,
SO42-
Write down the equilibrium equation
H2SO4 is a strong acid which dissociates
completely
2+
M gF − 2(s) ⇌ M g(aq)
∴ [H2 S O4 ] = [SO42− ] = 0.1
​

​ ​ ​

2F-(aq)
Use new conc. of SO42- and ignore original as it
is negligible
Write down the equilibrium expression to calculate new Ba2+

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K sp 1.0 × 10 −10 Partition coefficient (Kpc): equilibrium constant

that
[Ba2+ ] = = = 1.0 × 10 −9
​

[SO 2− ] 0.1 relates the concentration of solute partition between two

​ ​

4 ​

immiscible solves at a particular temperature.

Hence, solubility has decrease by a factor of 10 −4
C onc. of Solute in Solvent 1
K pc =
​ ​

C onc. of Solute in Solvent 2
3.11. Titration Curves
Place concentration of the first solvent mentioned on top of
the
Kpc expression

Kpc can be useful to work out how much solvent needed to

extract minimum amount of solute from one solvent to
another
Repeated extractions with smaller volumes of solvent
Titration: method used to find conc. of a solution by
more efficient
than one extraction with a larger volume.
gradually
adding to it a second solution of known conc.
until neutralization
point is reached  
Progress of neutralization reaction monitored using a pH Calculating Kpc
meter and
shown on a graph
100cm3 of a 0.100mol dm-3 solution of ammonia in
was
Equivalence point: mid-point of near-vertical portion of the
shaken with 50cm3 of an organic solvent and left in a
graph where no. of mols H+ = no. of mols OH-
separating funnel for equilibrium to establish
End point: volume of alkali/acid added when indicator just
changes colour A 20.0cm3 portion of the aqueous layer was run off and
Choosing a suitable indicator: titrated against 0.200mol dm-3 dilute hydrochloric acid. The
Sharp colour change at end point end-point was found to be 9.40cm3 of acid.
End point must be ±2 pH of equivalence point What is the partition coefficient of ammonia between these
Indicator should give distinct colour change two
solvents?
Solution
Colour at \n low pH Colour at \n high
Indicator Calculate conc. of aqueous layer run off (NH3(aq))
pH Range pH
NH3(aq) + HCl(aq)
NH4Cl(aq)
8.2 –
Phenolphthalein Colourless Pink 20.0cm3 9.40cm3
10.0
Use concentration of acid used to neutralize
Methyl orange Red 3.2 – 4.4 Orange
mols of NH3  in water
0.2 =
​

3.12. Solvents 9.4 × 10 −3

​

mols of NH3  in water = 1.88 × 10 −3

​

General solubility rule: like dissolves like

Covalent substances dissolve/mix in other covalent Use ratios to find moles of NH3(aq) in
100.0cm3
substances
Ionic substances do not dissolve/mix in other covalent 20.0cm3 : 1.88 × 10 −3 mols
substance
(exception is water)
Solubility in water 100cm3 : 9.40 × 10 −3 mols
Although covalent, highly polar nature makes it
excellent
solvent for ionic substances $\therefore$ moles of NH3 in water in equilibrium
$= 9.40
Dissolves some covalent substances because they \times 10^{- 3}$
either react or
form H-bonds with water molecules To find moles of NH3 in organic solvent, first find moles
present originally in the ammonia solution

3.13. Partition Coefficient initial mols of NH3  in water 

0.1 =
​

100 × 10 −3
​

Partition law: a solutes solubility will be differed in two

different liquids that are immiscible. The solute will be $\therefore$ moles of NH3 in water initially
$= 0.01$mols
more
soluble in one of the two. Subtract initial & final moles in water to find no. of mols in
Measured in [conc.]: g cm-3 or mol dm-3 organic
solvent = 0.01 − 9.40 × 10 −3 = 6.0 × 10 −4
When solute added to two immiscible solvents, a dynamic Calculate the Kpc value
6.0×10 −4
equilibrium
is set up where particles move between the K pc = conc. of NH∗3(org)
= 50×10 −3
​

conc. of NH∗3(aq) 9.4×10 −3
​ ​

two solvents but

concentration in each remains constant. 100×10 −3
​

Hence, can calculate a constant k for the equilibrium

K pc = 0.1277
​

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3.14. Working of an Alkali Buffer Half-life,

Order Graph of
t1/2
‎ ‎

‎[A]0 ‎Decreases

‎ ‎

[A]1 Constant
4. Reaction Kinetics
4.1. Rate of Reaction
‎ ‎
Rate of reaction is the change in concentration of
products/reactants per unit time
[A]2 ‎ Increases
[    ]
R= t ​                        Unit: mol dm-3 s-1

4.2. Rate Equation

Rate equations: states the relationship between the rate For zero order, rate of reaction not dependant on conc. of
constant and the concentrations of those reactants that
reactant but it is need for completion of reaction.
Reaction
continues until all of that reactant is used up.
xA  +  yB → P roducts Recognize shapes above in graphs given to work out
order of reactant
and construct rate equation. Calculate k
R = k [A]m [B]n using data from
graph(s).

Rate constant ( k): proportionality constant in

rate eqn. Constructing rate equation using conc. data:
Larger the rate constant, faster the reaction Using following data from the experiments construct a rate
Depends on temperature equation
and calculate rate constant.
Unit depends on overall order of reaction
Order of reaction ( m, n) : power to which conc.
of the
reactant is raised in experimentally determined rate eqn.
Solution
Overall order of reaction = m+n
Use data and deduce orders by looking at changes in conc.
Half-life, t 1 of a
reaction is the time taken for conc. of one and rates
(arrows added above):
2
Order of A = 1                           Order of B = 1
​

of the reactants to fall

by half
Write as rate equation

4.3. Order of Reaction R = k [A] [B]

Half-life, Calculate* k * using data given from e.g. experiment 1

Order Graph of
t1/2
R 4.0 × 10 −4 1
Conc./Time Rate/Conc. k= = =
[A] [B] 0.040 × 0.030 3
​ ​ ​

1
∴R= [A] [B ]
3
​

4.4. Calculating Rate Constant from t1/2

Only used with first order reactions

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Use the relationship: b. Write a rate equation for the reaction.

Solution
0.693
k= ​
Part (a)
t 12 ​
​

List all the reactants together and products together

Reactants: NO2 + F2 + NF2 +
NO2 + NF + O2
4.5. Relationship of Temperature and k Products: NF2 + O2 + NO2F +
NF + NO2F
Cancel the common things and form equation
Increasing the temperature, increases the value of k 2NO2 + F2 2NO2F
Part (b)
R Rate equation will include only reactants of slowest step
k=
[A] [B]
​

therefore:
When temp. is increased, the k.e. of reacting molecules R = k[N O2 ][F 2 ]
increases
resulting in more successful collisions
​ ​

Reactants change faster to products therefore conc. of

reactants
decreases. 4.7. Measuring Reaction Rates
Using fraction above, numerator increases and
denominator gets
smaller ∴ k increases. Sampling: method that involves taking
small sample of a
reaction mixture at various times and then carrying
out
chemical analysis on sample.
4.6. Reaction Mechanism
Chemical Analysis:
Rate-determining step: the slowest step in a reaction
mechanism C 4H9Br + OH-
C 4H9OH + Br-

  Sampled removed at various times and quenched –

In a multistep reaction: stopping/slowing
down reaction (e.g. cooling in ice)

The rate of reaction is dependent on the slowest step that OH- conc. can be found using titration
Plot graph and calculate rate of reaction
needs the
highest activation energy.
Rate equation includes only reactants that are present in  
the
rate-determining step. Continuous: method that involves
monitoring a physical
The orders with respect to the reactants are the moles of property over a period of time
the
reactants in the rate determining step
Change in Volume of Gas Produced:
 
Hydrolysis of Alkyl Halide Mg + 2HCl MgCl2 + H2

Primary alkyl halide mechanism:
C 3 H7 C H 2 B r  +  OH −
​ ​
Measure change in volume of gas using a gas syringe
slow Take down readings at regular intervals
​ ​ [C 3 H7 B rOH]
​ ​

Plot graph and calculate rate of reaction

f ast
[C 3 H7 B rOH]​ ​ ​ C 3 H7 C H2 OH + Br −
​ ​ ​
Changes in Colour:

∴ k[C 3 H7 C H2 B r][OH − ]
​ ​ ​
CH3COCH3 + I2
CH3COCH2I + HI

Tertiary alkyl halide mechanism: I2 starts brown, fades through orange to yellow to
colourless as iodine used up.
slow
(C H3 )3 C Br ​ ​ ​ (C H3 )C +   +  Br − ​
Colorimeter measures amount of light absorbed as it
passes through
solution; recorded as absorbance.
f ast
(C H3 )C +   +  OH −
​ ​ (C H3 )COH  +  Br − ​

∴ R = k[(C H3 )3 C Br] ​ ​

 
Constructing rate equation for multistep
reaction
The mechanism for the production of NO2F involves
slow
NO2 + F2 ​ NF2 +
O2 ‎
f ast
NF2 + NO2 NO2F + NF
Before experiment, create calibration curve by finding
​

f ast
NF + O2 NO2F ​

absorbance of
different conc. I2 and plot a graph of
a. What is the overall stoichiometric equation?

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concentration
against absorbance
4.11. Examples of Heterogeneous
During experiment, measure absorbance from meter at
regular
intervals, and use calibration curve to convert Catalysis
values into
concentrations
Iron in Haber process:

4.8. Homogeneous Catalysis N2 + 3H2

​ ​
Fe
​ 2N H3 ​

Catalyst and reactants in same physical state

Catalyst takes part in reaction:
Forms intermediate with reactant Diffusion of
Intermediate breaks down giving product N2 and H2
Rate of reaction dependant on conc. of catalyst to the
surface of
4.9. Examples of Homogenous Catalysis iron

Iodine-Peroxydisulfate Reaction ‎

S 2O82- + 2I- $\xrightarrow{slow}$

2SO42- + I2 Adsorption;
bonds
Mechanism of the catalysed reaction: formed
between
Reaction 1: reduction of Fe3+ to Fe2+ ions
by I- ions
reactant
2I- + 2Fe3+ $\xrightarrow{Low\ Ea}$ I2 + 2Fe2+ and iron:
Reaction 2: oxidation of Fe2+ to Fe3+ ions by strong
S 2O82- ions enough to
weaken
S 2O82- + 2Fe2+ $\xrightarrow{Lower\ Ea}$
2SO42- + 2Fe3+ covalent
bonds
within ‎
N2/H2,
weak
enough to
break and
allow
Oxides of Nitrogen and Acid Rain products to
leave
Reaction;
adsorbed N
and H
atoms
react to
form NH3 ‎
SO3 can then react with water to form
H2SO4
Desorption;
bonds
4.10. Heterogeneous Catalysis break
between
Catalyst and reactants in different physical state NH3 and
Catalyst provides surface on which reaction occurs ‎
surface
Reactant particles adsorbed on surface on collision
with
catalyst Diffusion of
Molecular rearrangement occurs - bonds in reactants NH3 away
break and
new bonds in product formed from
Product molecules desorbed from surface surface of
Rate of reaction dependant on surface area of catalyst iron ‎
Adsorption: weak bonds formed between reactant
molecules &
surface of catalyst (diffusion on to surface) png)
Desorption: releasing of product molecules from surface
of
catalyst (diffusion away from surface)

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Honeycomb structure containing small beads coated with

Pt, Pd and Rh
Possible catalytic process:
Adsorption of NOx and CO
Weakening of covalent bonds within NOx and CO
Formation of new bonds between
Adjacent N atoms form N2
CO and O atoms form CO2
Desorption of N2 and CO2

5. Chemistry of Transition
Elements ‎

Transition element: a d-block element that forms one or d xy , d xz and d yz have

d-orbitals in between axis
​ ​ ​

more
stable ions with incomplete d orbitals d x2 −y2 and d z 2 have d-orbitals along
axis
​ ​

d z 2 is formed by the merging of d x2 −z 2

and d y2 −z 2
​ ​ ​

5.2. Electronic Configurations

5.4. Physical Properties
Element Electronic Config. Oxidation States
Sc, scandium [Ar] 3d 1 4s2 +3
Ti, titanium [Ar] 3d 2 4s2 +3, +4
V, vanadium [Ar] 3d 3 4s2 +2, +3, +4, +5
Cr, chromium [Ar] 3d 5 4s1 +3, +6
Mn, manganese [Ar] 3d 5 4s2 +2, +4, +6, +7
Fe, iron [Ar] 3d 6 4s2 +2, +3
Co, cobalt [Ar] 3d 7 4s2 +2, +3
Ni, nickel [Ar] 3d 8 4s2 +2
Cu, copper [Ar] 3d 1 04s1 +1, +2
Zn, zinc [Ar] 3d 1 04s2 +2

Scandium and Zinc are not transition metals because:

Sc3+ has no e-s in the d-orbital
Zn2+ contains a full d-orbital
Chromium and copper have anomalous configurations ‎
Cr: 4s electron demoted to half-fill 3d shell
Cu: 4s electron demoted to full-full 3d shell
creating a more stable configuration.
5.5. Variable Oxidation States
When electrons added, fill 4s before 3d
Small energy difference between 4s and 3d so electrons
When electrons removed, remove from 4s before 3d
from both
subshells can be removed to form a variety of
oxidation states
5.3. d-Orbitals All transition metal exhibit two or more oxidation states
Most common oxidation state +2 when 2e-s from 4s lost
Transition elements show highest oxidation states when
they combine
with O or F (most electro-ve)
When transition elements form compounds with high
oxidation states
above +4, they form large oxyanions and
are covalent (acidic oxides)
e.g. CrO4- or MnO4-
When transition elements in lower oxidation states they
form ionic
compounds (basic oxides)

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For bi and polydentate ligands, use prefixes mono-,

5.6. Complexes
bis-, tris-,
tetrakis-, pentakis-
Name the ligands
Complex: is an ion or molecule formed by a central metal
If neutral and -ve ligands present, first name -ve ligand
atom/ion surrounded by one or more ligands
If ligands all neutral/-ve or contain more than one of
A complex consists of:
each,
name in alphabetical order
Central transition metal ion (+ve) that can accept
e-s
Ligand (-ve): a species that contains a lone pair of
e-s Anions Neutral Ligands
that forms a dative bond to a central metal
atom/ion Amine (NH3)
Fluoro (F-), Chloro (Cl-)
Coordination no.: number of coordinate or dative bonds to
the
central metal atom/ion Cyano (CN-) Aqua (H2O)
Different metal ions show different coordination number Hydroxo (OH-)
with same
ligands
Transition metals form complexes because
Name central metal ion
Ion are small in size so they have a strong electric field If complex ion +ve/neutral – use normal name
around them which attract e--rich ligands If complex ion –ve, use name ending –ate; special:
They have empty 4s and 4p orbitals that are Iron = Ferrate
hybridised and can
accept e- Lead = Plumbate
Copper = Cuprate
Oxidation no. of metal ion in Roman numeral and ‘ion’
5.7. Ligands
Monodentate ligands: forms only one coordinate bond
with central
metal ion (donates one pair of e-s)

Anions Neutral Ligands

Halide ions F-, Cl-, Br-, I- Water H2O
Sulphide S2- Ammonia NH3 ‎
Nitrite NO22- Carbonyl CO
Hydroxide OH- 5.9. Writing Formulae of Complexes
Cyanide CN-
Metal ion written first followed by ligand
Thiocyanate SCN- Place charge on formula in square brackets
Total charge on complex = sum of charge on metal
Bidentate ligands: forms 2 coordinate bonds with central ions and charge
on ligand
metal
ion (donates 2 pairs of e-s per molecule) If ligands all neutral, charge on complex = charge on
metal ion

5.10. Shapes of Complexes

‎ Coordination No.

Diagram
H2N – CH2 – CH2 – NH2 -O – CO – CO – O- & Shape

Ethylene diamine (en) Oxalate ion

(neutral) (oxalato-) 6

Octahedral
png" width=20%>
\[Fe(H2O) 6\]2+

Forms 6 coordinate bonds

4 from oxygen
2 from nitrogen
4

Tetrahedral
5.8. Writing Names of Complexes
\[CoCl4\]2-

To represent coordination number 4

For monodentate ligands, use prefixes mono-, di-, tri-, Square
Planar
tetra-,
hexa- (most Ni and Pt)

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Not ligand exchange; hydroxide ions remove hydrogen

ions from water
ligand

 

Reaction with Ammonia Solution
\[Ni(CN) 4 \]2-
Small amount of ammonia
2

Linear
\[Ag(NH3) 2\]+

Initially, ammonia acts as a base and hydrogen ions are

5.11. Stereoisomerism pulled off
the hexaaqua ion as above.

Excess ammonia
Geometric isomerism (cis-trans)
Pt(NH3) 2Cl2

Ammonia replaces water as a ligand

Only 4 of the 6 water molecules replaced

 
Reaction with Chloride Ions
cis-platin trans-platin

Cis-platin is an anticancer drug that acts by binding to

DNA in
cancer cells, preventing cell division 6 water molecules replaced by 4 chloride ions

 
Optical isomerism 5.14. Ligand Exchange and Stability
[N i (N H2 C H2 C H2 N H2 )3 ]
​ ​ ​ ​ ​
Constant
Ligand exchange: a more powerful ligand will substitute a
less
powerful ligand from a cation of the complex and this
can produce a
change in colour and shape

Strength of Different Ligands:

EDTA > S - > CN- > I- >
S 2O32- > Br- >
NH3 > Cl- > H2O

Exchange of ligands can be explained in terms of

5.12. Common Complexes completing
equilibria of forward & backward reaction
Equilibrium position lies towards more stable complex
Ligand Cu(II) Co(II) Adding excess weak ligand can shift equilibrium backward
and form
weaker complex
H2 O [Cu(H2O)6 ]2+ [Co(H2O)6]2+ Stability constant, Kstab: the equilibrium constant
for the
NH3 (drops) Cu(H2O) 4(OH) 2 Co(H2O) 4(OH) 2 formation of the complex ion in a solvent from its
constituent ions or molecules
NH3 (excess) [Cu(NH3)4(H2O)2 ]2+ [Co(NH3)6 ]2+
Water not included in Kstab expression because
OH- Cu(H2O) 4(OH) 2 Co(H2O) 4(OH) 2 concentration almost constant
Cl- [CuCl4]2- [CoCl4]2-
e.g. [Cu(H2O) 6]2+ +
4Cl- ⇌ [CuCl4]2- + 6H2O

5.13. Copper Chemistry [[CuCl4 ]2− ]

K stab =
​

2+ 4
[Cl− ]
​ ​

[[C u(H2 O)6 ]

Reaction with Hydroxide Ions
​ ​

Units = mol-4 dm12

Stability constants are used to compare stability of any

two ligands

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The greater the Kstab value, the more stable the complex Small ΔE = light absorbed from red = complex
blue-ish
Kstab values may be given on log 10 scale as
values large
Stability constants for complexes with bi/polydentate
ligands very
high
6. Arenes
5.15. Colour of Complexes 6.1. Bonding in Benzene Ring
The five d-orbitals in isolated transition metal atoms/ions
are
degenerate; all at the same energy
Coordinate bonding from ligands cause five d-orbitals to
split into
two sets of non-degenerate orbitals at ΔE
For octahedral complexes, ligands approach along axis
and increases
repulsion with d x2 −y 2 and d z 2 orbital
causing them to be at higher energy C – C bond length equal = 0.139nm

Benzene is a symmetrical flat hexagonal planar molecule

e.g. an octahedral complex of Cu2+
Consists of 6 C – C single bonds and remain electrons
exist in
delocalized system
All C – C bonds are the same length (0.14nm) which are
smaller than
a single bond but greater than a double
Each carbon forms 3 sigma bonds ( sp 2 hybrid)
2 between carbon and carbon (on either side)
Electrons from lower energy orbitals absorbed energy 1 between carbon and hydrogen
equal to
ΔE from light and are excited to a higher A p-orbital from each C atom overlaps above and below
energy
level orbital the plane of
the ring forming two continuous loops; each C
atom donates 1
electron into this π bond (delocalized)

6.2. Properties of Benzene

Clear, colourless, non-polar liquid at r.t.p
It is volatile and has a low b.p.
Wavelengths of light equivalent to ΔE are absorbed
and Relatively unreactive due to strong bonding
the rest are transmitted. Burns with smoky flame
Wavelengths transmitted merged together corresponds
to the colour of
the solution observed
6.3. Naming Aromatic Compounds
Conditions for complex to be coloured:
At least one d-orbital must be occupied by an e- Name with Benzene Name with Phenyl
At least one d-orbital must not be fully occupied
Hence, some compounds of d-block metals colourless:
All Sc compounds colourless because [Ar] 3d0 ‎
All Zn compound colourless because [Ar] 3d10 Phenol

Factors that determine colour of complex (which affects Chlorobenzene

the
splitting of d-orbitals):
Magnitude of ΔE
Strength of ligands ‎
Oxidation state of metal ion ‎

Phenylethene
Geometry of complex Methylbenzene

Colour Spectrum
                 wavelength increases                  ‎
​
‎ Phenylamine
                 f requency and energy increases                  Nitrobenzene

R O Y G B I V

Phenyl ethanoate

Large ΔE = light absorbed from blue = complex

red-ish
Benzoic acid

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Generating electrophile:
6.4. Electrophilic Substitution
2H2SO4 + HNO3 → 2HSO4- + NO2+ + H3O+
Mechanism Regenerating catalyst:

An H-atom on the ring can be substituted by other 2HSO4- + H3O+ +

H+→ 2H2SO4 + H2O
atoms/groups
Alkylation / Acylation
All carbon atoms identical and benzene ring symmetrical
hence any
H-atom can be substituted AlCl3
C 6H6(l) + RCl/RCOCl
C 6H5R/C 6H5RCO +
HCl(g)
​

An electrophile (E+) can attack the ring of π

e-s but Reagent:
benzene highly stable so E+ must be
very strong. alkyl halide (RCl) / acyl chloride (RCOCl)
A +ve ion can be generated by heterolytic fission of a Condition:
covalent bond
hence catalyst needed to generate E+ Temp.: heat under reflux
Catalyst: anhydrous AlCl3
  Generating electrophile:
Mechanism: AlCl3 + RCl/RCOCl [AlCl4]- +
R+/RCO+
Regenerating catalyst:
H+ + [AlCl4]- HCl +
AlCl3

6.6. Electrophilic Addition Reaction

Hydrogenation
E+ attacks π e- ring, accepting a pair
of e- from benzene
Nickel
An intermediate +ve specie is formed in which +ve charge C 6H6(l) + 3H2(g)
C 6H12
​

is
delocalized around the ring (more stable than a normal Type of reaction:
carbocation) electrophilic addition
Proton eliminated from +ve intermediate to restore Conditions:
stability and
π system of delocalized e-s reformed Temp.: 150ºC
Catalyst: nickel
6.5. Electrophilic Substitution
Reactions 6.7. Side Chain Reactions
Chloromethyl Benzene
Halogenation
catalyst C 6H5CH3(l) + Cl2(g) →
C 6H5CH2Cl(l) + HCl
C 6H6(l) + X2(g/l)
C 6H5X(l) + HX(g)
Type of reaction:
Reagent: free radical substitution
dry Cl2 gas / pure Br2 liquid Reagent:
Conditions: Cl2(g)
Temp./press.: r.t.p. Condition:
Catalyst: anhydrous AlCl3(s) / FeBr3(s) u.v. light
Generating electrophile: With excess Cl2 a mixture of di, tri chloromethyl benzene
catalysts are e- deficient halogen carriers, form
dative can be obtained
bond drawing e- from halogen molecule
producing X+
 
AlCl3 + Cl2 → [AlCl4]- +
Cl+ Benzoic Acid
Regenerating catalyst:
H+ + [AI C l4 ]− ​ → HCl + AlCl3 C 6H5CH3(l) + 3[O] →
C 6H5COOH(l) + 2H2O
Type of reaction:
Nitration oxidation
Reagent:
C 6H6(l) +
H2SO4/HNO3 →
C 6H5NO2(l) +
H2SO4(g) + H2O KMnO4(aq) or
K2Cr2O7(aq)
Reagent: Condition:
nitrating mixture heat under reflux (2 to 3 hours)
conc. HNO3 / conc. H2SO4 Alkyl gp. always oxidized regardless of chain length
Condition: If more than one alkyl gp., each one oxidized
Temp.: 45-55oC under reflux

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Condition:
6.8. Ring Activating/Deactivating
Temp.: 300-330oC
Groups Press.: 150-300 atm
Rate of Hydrolysis: (slowest to fastest)
Ring Activating Ring Deactivating
Alkyls, NH2, OH Cl, NO2, COOH

Donates e- to the ring Withdraws e- from ring ‎

+ve inductive effect
electro-sub faster
Increase e- density at position
2 and 4
both corrosive and anaesthetic
substituents attached at positions 2,4 and 6
-ve inductive effect
electro-sub slower
8. Phenol
Sub. occurs at pos. 3 & 5
Phenol is an aromatic alcohol; a white crystalline solid that
is
OH group is ring activating so phenol more reactive than
benzene and

8.2. Solubility and Acidity of Phenol

7. Haloarenes
7.1. Reactivity of Benzene &
Chlorobenzene ‎

OH group forms H-bonds with water molecules however

Chlorobenzene is less reactive than benzene because:
there are weak
VDW forces due to heavy nonpolar
Chlorine is a ring deactivating group benzene ring hence phenol partially
soluble in water
Chlorine is more electronegative than carbon, and draws Solution of phenol is slightly acidic because –OH in phenol
electrons in
the ring towards itself. breaks
to form H+
Hence electron density around ring decreases, less Bond breaks readily because phenoxide ion formed is
attractive for
electrophiles and so reaction is slower stabilized by
partial delocalization of –ve charge over the
benzene ring
7.2. Reactivity of Haloarenes &
Haloalkenes
The halogen atom in halogenoarene is much less reactive
than that in a
halogenoalkane
The conjugate base (phenoxide) is stable and less likely to
Lone pair of e‑ s of Cl overlap slightly with p
orbitals of react
with H+ going back to phenol
benzene ring giving C–Cl a double bond character
Makes C–X bond much stronger therefore nucleophilic
substitution
difficult
8.3. Acid-Base Reactions
High density of e-s on benzene ring tends to repel the Reaction with Base
approaching –ve charged nucleophile.
r.t.p
C 6H5OH(l) + NaOH(aq)

C 6H5O-Na+(aq)
​

7.3. Nucleophilic Substitution Reaction H2 O

Type of reaction:
Hydrolysis Neutralization
Reagent:
C 6H5Cl(l) + NaOH(aq)
→ C 6H5OH(l) +
NaCl(aq)
sodium hydroxide
Type of reaction: Condition:
nucleophilic substitution r.t.p.
Reagent: Regenerating phenol:
sodium hydroxide

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When strong acid (HCl) added to solution of sodium

phenoxide,
phenol regenerated
C 6H5O-Na+(aq) + HCl(aq)­ →
C 6H5OH(l) + NaCl
Initially dense white emulsion formed then slowly oily
liquid
layer of phenol separates

 
Reaction with Sodium
r.t.p 8.5. Relative Acidities
C 6H5OH(l) + Na(s)
C 6H5O-Na+(aq) + ½H2(g)
Type of reaction:
metal and acid, redox
Condition:
r.t.p.
‎
Reacts with Na liberating H2 gas
Note: phenol does not react with metal carbonate to The stronger the acid:
liberate
CO2 hence shows its fairly weaker than other Higher the Ka value
carboxylic
acids More easily H+ is donated
More stable is the conjugate base
8.4. Reaction with Benzene Ring
 
Ethanol: C 2H­5OH + H2O
⇌ C 2H5O- +
H3O+

Ka : 10-18 mol
dm-3
Ability to donate H+ ions:
C 2H5 is an e- donating gp.
which increases charge
density on O of OH
Bromination

More attraction between O–H so loss of H+ difficult

Type of reaction:
electrophilic substitution Stability of conjugate base:
Reagent: In ethoxide ion, C 2H5 gp. increases –ve
charge
aq. Bromine Makes ethoxide ion more basic than OH-
Condition: Ability to accept H+ increases, moving equi. to left
r.t.p. (no catalyst)
Rapid reaction, forms a white ppt.
No catalyst needed since Br2 molecule easily polarized by ‎
increase e- density in ring  
Water: H2O + H2O ⇌
OH- + H3O+
 
Nitration Ka : 10-16 mol
dm-3
No e- donating or withdrawing gp. present hence ability
to
donate and accept H+ ion is the same
Type of reaction:
electrophilic substitution  
Reagent: Phenol: C 6H­5OH + H2O
⇌ C 6H5O- +
H3O+
dilute nitric acid
Condition: Ka : 10-10 mol
dm-3
r.t.p. Ability to donate H+ ions:
If concentrated nitric acid used, then trinitrophenol
OH is a ring activating gp. & the lone pair of e-s on
O
produced
becomes part of delocalized e- system

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Decreases e- density on O of OH and attraction more susceptible to attack by a nucleophile

between O and H decreases so H+ lost more easily

Stability of conjugate base:
In phenoxide ion, -ve charge on O delocalized around
ring and
reduces tendency to attract H+
Conjugate base stable

8.6. Test for Phenol

Test 1:
9.3. Nucleophilic Condensation
Mechanism
Reagent: Iron(III) Chloride
(FeCl3(aq)) – yellowish brown
Observation: violet colour obtained

Test 2:

Reagent: bromine water

(Br2(aq)) – orange
Observation: white ppt. obtained

9. Acyl Chlorides
9.1. Preparation of Acyl Chlorides
‎
‎
The carbonyl carbon being highly e- deficient is attacked
by nucleophile
The Nu bonds to the carbon atom, the C = ­O bond is
broken leaving
O with –ve charge
Chloride is lost and carbonyl double bond is reformed

9.4. Nucleophilic Condensation

These are derivatives of carboxylic acids; -OH gp. of acid
replaced
by Cl Reactions
Named after corresponding acid using suffix –oyl followed
by
chloride Hydrolysis
e.g. ethanoyl chloride

Forming Amides

Primary amides:
R—CO—Cl + NH3 →R—CO—NH2 + HCl
Reagent: ammonia
Secondary amides:
R—CO—Cl + R’NH2 → R—CO—NHR’ + HCl
Reagent: alkyl amine
Note: If excess NH3 used,
the HCl formed is neutralized to
‎ NH4Cl

 
9.2. Reactivity of Acyl Chlorides Esterification

Acid chlorides are much more reactive than the carboxylic R—CO—Cl + HO–R → R–CO–OR(aq) + HCl(aq)
acid from
which they are derived Reagent & Condition:
Polarity of both C = O and C—Cl bond produces relatively Aliphatic alcohol at r.t.p
large
δ + charge on the carbon, making it e- deficient
and Phenol dissolved in NaOH, warm it

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Hydrolysis of esters: Alkyl groups increase –ve charge on ion formed when
dissociated,
making it easier to accept the H+ and reform
the molecule

10.3. Chlorine Substituted Acids

9.5. Relative Ease of Hydrolysis Acidity of carboxylic acids increases when H atoms are
substituted by
electro-ve (withdrawing) atoms e.g. Cl
− Increasing ease of hydrolysis→
Chlorine atoms show a –ve inductive effect withdrawing –
Alkyl
Aryl Chlorides Acyl Chlorides ve charge
from the molecule, reducing the strength of the
Chlorides
O–H, and hence
making H+ be lost more easily
R–Cl Conjugate base is more stabilized due to the extended
‎
delocalization
of the negative charge on the –COO- and so
Aryl chlorides do not undergo hydrolysis at r.t.p because less likely to
bond with a H+ ion
the
p-orbitals from chlorine overlap with delocalized p-
 
electrons giving
the C–Cl bond a double bond character
Note:
Alkyl chlorides require a strong alkali (NaOH) under reflux
to
be hydrolysed as carbon doesn’t have a high δ +
If an e- donating gp. present molecule less acidic
Acyl chlorides undergo hydrolysis with neutral water at
r.t.p
because the carbon atom is bonded to two highly If an e- withdrawing gp. present molecule more acidic
electronegative
atoms hence has a high δ + therefore
attack by a nucleophile
is much more rapid 10.4. Oxidation of Carboxylic Acids
Acid + Oxidizing Agent (warm) $\rightarrow$ CO2 + H2O
10. Carboxylic Acids Methanoic Acid

Carboxylic acids are weak acids and dissociate HCOOH + [O] → CO2 + H2O
incompletely in
aqueous solutions With Tollens’ Reagent:
Ag + gets reduced to silver – silver mirror formed
R–COOH + H2O
With Fehling’s Solution:
⇌
Cu2+ gets reduced to Cu+ – copper(I) oxide
(red)
R–COO- +
H3O+
Note: can use stronger [O] agents; Mn or Cr
The O–H bond in carboxylic acid is weakened by the
 
carbonyl group
C = O
Ethanedioic Acid
The carboxylate ion is stabilized by the delocalization of
e-
s around the –COO- group, spreading and
reducing the
density of -ve charge making it less likely to bond
with H+

HOOC–COOH + [O] → CO2 + H2O

With warm Acidified Manganate(VII) - KMnO4/H+:
Purple/pink to colourless
Note: can also use Acidified Dichromate(VI)
Changes from orange to green
10.2. Relative Acidities of Carboxylic
Acids 11. Nitrogen Compounds
Acidity of carboxylic acids decreases as carbon chain length Primary Amine Secondary Amine Tertiary Amine
increases
because:

Alkyl groups are e- donating groups which have a +ve

inductive effect increasing strength of O–H bond, and
making it more
difficult to donate H+

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Primary Amine Secondary Amine Tertiary Amine

‎

11.5. Relative Basicity

‎

11.2. Formation of Alkyl Amines

Substitution
Phenyl amine weaker Ethylamine stronger
R–X + NH3 → R–NH2 + HX(g) than ammonia than ammonia
Type of reaction:
nucleophilic substitution ‎
Reagent:
Lone pair of e-s on N gets
hot conc. NH3 in ethanol Ethyl e- donating group,
partially delocalized by
Condition: increases e- density on
interaction with benzene
heat under reflux N
e- cloud Ammonia
Reduction Enhanced ability to
R–CO­–NH2 + 4\[H\] → R– Lone pair less available
R–C ‎≡‎N + 4\[H\] ‎→‎R–CH2NH2 for coordination to proton donate lone pair of e-s
CH2NH2 + H2O to proton
Type of reaction: reduction of Type of reaction: reduction of Alkyl ammonium cation
a nitrile an amide formed more stable
Reagent: hydrogen gas Reagent: hydrogen gas than NH4+ cation from
Reducing Agents (catalyst): ammonia
Reducing Agent (catalyst):
LiAlH4 in dry ether
LiAlH4 in dry ether
Nickel
11.6. Reactions of phenyl amine
Conditions: high temp. and
Conditions: r.t.p.
pressure Bromination

11.3. Formation of Aryl Amines

Reduction
Type of reaction:
electrophilic substitution
Reagent:
aq. Bromine
Conditions:
Type of reaction: r.t.p. (no catalyst)
reduction of nitrobenzene Forms a white ppt.
Reagent:
conc. HCl with Tin  
Condition: Diazotization
heat

11.4. Basicity of Amines

Bases are proton acceptors (electron donors) (–N2+ is called diazonium ion)
N-atoms in amines have a lone pair of e-s
Type of reaction:
N donates lone pair and accepts H+ forming dative bond
diazotization reaction
Reagent:

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nitrous acid (NaNO2 with excess HCl(aq)) ‎

(HNO2 weak, unstable acid so produced by reaction
NaNO2 with excess HCl)
Condition:
low temp. (5∘ C) ethanoyl chloride + methyl amine → N-methyl
Note: methanamide
Diazonium salts of aryl amine stabilized by
delocalization of
–N2+ ion’s e-s over benzene
ring 11.9. Neutrality of Amides
However, diazonium ion highly unstable and can
decompose above
10oC to The presence of the electron withdrawing oxygen atom
means that the
lone pair on the amide’s nitrogen atom is
not available to be
donated to e.g. H+ ions
Hence, amides are neutral

11.7. Coupling Reactions of Diazonium

Salts
11.10. Hydrolysis of Amides
Type of reaction: electrophilic substitution
Reagent: aromatic amines or phenols
Azo compounds are complex compounds involving a
minimum of two
aromatic rings joined by N=N coupling
Benzene diazonium ion carries a +ve charge and readily
reacts with
cold alkaline solutions of aromatic amines and
phenols to give
brightly coloured azo-compounds

Bright orange dye formed

11.11. Amino Acids
By using alterative aryl compounds to phenol, a range of
brightly
coloured dye can be formed.

11.8. Formation of Amides

Formation Optical activity: all amino acids (except glycine) have a
chiral
carbon therefore they are optically active
Primary Amides:

11.12. Acid/Base Properties of Amino

Acids
Secondary Amides: Basic amino group and acidic carboxyl group interact:
Carboxyl group donates a proton to amino group
Amino group accepts proton and zwitterion formed
Type of reaction:
nucleophilic substitution
Reagent:
conc. NH3(aq)
Condition:
r.t.p.
Example:

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Zwitterion: ion that contains regions of +ve & –ve charge

Amino acids solids at r.t.p. due to ionic bonds that exist
between
zwitterions
Presence of zwitterions means that amino acids are
soluble in water

Sample placed on absorbent filter paper (or gel)

11.13. Amino Acids in Acidic/Basic Buffer solution carries ions along (back or forth)
Conditions
Factors that Determine the
Direction of Travel Speed of Movement
If acid added, the –COO- part of the zwitterion accepts
an
Voltage applied
H+ ion, reforming –COOH group, leaving +ve charge
pH of buffer solution Temperature
If alkali added, the –NH3+ part of the
zwitterion donates Charge on amino acid Size (Mr) of amino acid
an H+ ion to the OH-,
reforming –NH2 group and H2O, Magnitude of charge
leaving a -ve
charge Larger ions with longer side chain move slower
More highly charge ions move faster

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12. Polymerisation
12.1. Addition Polymerisation

11.14. Peptide Bonds Monomers are alkenes; polymer formed is polyalkene

Alkene joins to itself, no molecule lost
Amide link formed by nucleophilic attack of –NH2 group of E.g. nA →   −A − A − A − A− or (−A−) ­ n ​

one amino acid on –COOH group of another Molecular mass of polymer is multiple of monomer

 
Physical Properties of Polymers:

Only C and H present = only VDW forces present

Presence of Cl or F = dipoles = permanent dipole
interaction
Longer chains with have fewer side chains have stronger
Reaction is a condensation reaction as H2O eliminated VDW forces
Reaction can continue to occur as product still has –NH2
and –COOH group present

Dipeptide → Tripeptide → Polypeptide (protein)

Proteins are polymers of amino acids; many polypeptide ‎ ‎

chains held
together by intermolecular forces polyethene polytetrafluoroethene
Hydrolysis: involves breaking of peptide links by reaction
with
water catalysed by an acid or alkali catalyst, giving LDPE HDPE
back the amino
acids, temp. nearly 90oC Soft plastic made with non-
Using Ziegler catalyst
polar polymer
11.15. Electrophoresis Hard plastic made with non-
Highly branched chains
polar polymer
Electrophoresis is used to separate, identify and purify Low melting point Unbranched chains
amino
acids obtained when protein hydrolysed
Chains cannot pack closely
Technique based on separating ions placed in an electric
due to random branching High melting point
field. When
sample placed between two electrodes:
leaving gaps
+ve charge ions move towards –ve charged electrode
–ve charge ions move towards +ve charged electrode Closely packed chains, less
= low density
gaps

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LDPE HDPE
= high density

12.2. Natural and Synthetic Rubber

‎
Rubber is formed (naturally and synthetically) by addition
polymers Used for spinning into fibres

  12.5. Examples of Polyamides

Natural Rubber:
Synthetic polyamides: Nylon and Kevlar
Natural polyamides: proteins

 
Nylon 6, 6

isoprene natural rubber Monomers:

12.3. Condensation Polymerization

When two different molecules (monomers) react together
‎
to form an
ester or amide bond with the elimination of a
Hexandioic acid 1, 6-diaminohexane
small molecule
(H2O or HCl)
Polymer:
Polyamides Polyesters
Monomers joined by ester
Monomers joined by amide
link:
(peptide) link:

‎
 
Nylon 6
12.4. Examples of Polyesters
Monomer: contains both NH2 and COOH group
Synthetic polyesters: terylene Caprolactam is a cyclical compound and when heated
Natural polyesters: fats at
260oC, cycle breaks and polymerizes
 
Terylene
 
Caprolactam nylon 6
Monomers:  
Properties of Nylon:

High tensile strength: due to H-bonds between chains of

polymers;
the N and O atoms with H
Ethane-1, 2-diol 1
Elasticity: single covalent bonds within polymer, chains
are free to
rotate
Low density: unbranched chains, no gaps

4-benzenedicarboxylic acid Hence very useful fibre in clothing industry

 
Polymer:
Kevlar:

Monomers:

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Functions of deoxyribonucleic acid (DNA):

Can make copies of itself so that genetic information can

be pass on
from generation to generation
Contains sequence of bases that form genetic code used
to synthesize
proteins

Benzene-1, 4-diamine benzene-1, 4-dioic acid  

Nucleotides in DNA are made up of:
Polymer

A sugar called deoxyribose

A phosphate group
A nitrogen-containing base
Extremely strong: delocalization of π e-s beyond
benzene
ring on to amide link, enhanced intermolecular bonding  
between polymer chains Nitrogen-containing bases:
Flexible, strong, fire resistant and low density Double Rings Single Ring
Hydrogen bonding between chains:

‎ ‎ ‎ ‎
adenine guanine thymine cytosine

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12.6. Proteins
12.8. DNA Replication
Proteins: a natural polyamide; many polypeptide chains
held together
by intermolecular forces
Process of copying DNA during cell division
Amino acid residue: an amino acid unit within a
polypeptide chain  
Semi-conservative replication:
 
Examples of Amino Acids: H-bonds and VDWs between base pairs in part of a DNA
Non-Polar R-Group: Polar R-Group: are broken and
this part of the double helix unwinds
In the nucleus, there are nucleotides to which two extra
phosphates
have been added (nucleotide triphosphate)
The bases of the nucleotide triphosphates pair up with
complimentary
bases on the old strand and H-bonds &
VDW forces form between
original and new strands.
Enzymes catalyse the polymerization reaction
alanine serine
valine cysteine Each new strand contains a sequence of bases that is
Electrically Charged R-Group: complimentary
to the original strand e.g.

Original strand: – A T G C C G T T A A G T –
New strand: – T A C G G C A A T T C A –

‎
aspartic acid lysine

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‎
12.7. Structure of DNA
Significance of H-bonding in replication of DNA:
DNA are polynucleotides; made by condensation When a new strand built on template of old strand, the
polymerization of
nucleotides. incoming
nucleotide is selected for its ability to pair
with base in the
old strand
 

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H-bonding plays an important role in the recognition

as
different number of H-bonds involved in each pair

12.9. Non-solvent based Adhesives ‎

Silyl modified polymers (SMP): Contains alternate single & double carbon-carbon bonds
Can conduct electricity because p-orbitals on
neighbouring carbon
atoms overlap resulting in long
bands of delocalized π
e-s free to move along the chain
Doping: other substances, such as iodine, added to
improve
electrical conductivity of polymer
Advantages over metal conductors:
Do not corrode
A polymer that contains silicon bonded to oxygen
Much less dense
They set by reacting with moisture in air; water hydrolyses
silicon-oxygen parts, forming cross-linkages Shaped more easily
E.g. made into thin sheets to make flat panels that light
Effectively bonds polymer chains to each other with
strong covalent
bonds of siloxane cross-linkage
12.11. Degradable Polymers
 
Epoxy Resins: Disadvantages of plastics:
Non-biodegradable
Example of thermosets: polymers that form extensive
On combustion, give out harmful vapours
networks of
covalent cross-links
Very strong and cannot be melted and remoulded  
Formed by reacting a monomer with expoyethane Biodegradable Plastics:
(triangular molecule
CH2CH2O) and a diamine are mixed
For example: Can contain small amounts of starch: bacteria and fungi in
moist
soil can break it down into smaller compounds,
increase surface area
and easier to decompose
Can be made from monomers derived from plants e.g.
PLA: soil
microorganism can digest it easily
Can be hydrolysed in acidic conditions:
The polymer produced forms a giant network of cross- Polyamides broken down to carboxylic acids & amines
linking with
other polymers: Polyesters broken down to carboxylic acids & alcohols

 
Photodegradable Plastics:

Carbonyl group (–C = O) can absorb energy from

ultraviolet waves
Causes bonds in region of carbonyl group to weaken and
Superglue: break
Disadvantages:
Uses addition reaction to stick objects together Plastic usually buried under ∴ cannot get sunlight
The monomer is CH2­= C(CN)COOCH3, methyl If recycled, products are weaker
cyanoacrylate, and addition takes place across C = C

13. Entropy & Gibb’s Free

Energy
Polymerisation initiated by presence of moisture 13.1. Entropy Change
12.10. Conducting Polymers Entropy: measure of the ‘disorder’ of a system
A system becomes more stable when its energy is spread
Polymers generally insulators but ethyne can conduct out in a more
disordered state
electricity Spontaneous change: a change that tends to happen
naturally;
once started, the change will carry on

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Spontaneous changes may not be instantaneous or At position of equilibrium, the total entropy change of
happen rapidly; most
are slow and need an input of forward
reaction equals the total entropy change of
energy to start backward reaction
Under standard reactions, the overall entropy change is
13.2. Changing Entropy zero

As a substance changes state from (s) → (l)

→ (g); its 13.6. Gibbs Free Energy
entropy increases as molecules become more
disordered
When an ionic salt is dissolved in water (s) → (aq);
the ΔG = −T ΔS total ​

entropy increases as as the crystal breaks up and the ions

find
their way between the water molecules Gibbs free energy ( G ): amount of energy in a system that
Increasing the temperature of a substance (without is available to do useful work
changing state)
increases entropy e.g. when heating a Standard molar Gibbs free energy of formation
( ΔG θf ): ​

gas, the number of different

possibilities for arranging the the free energy change that accompanies the formation
energy over the molecules increases. of one mole of a compound from its elements in their
If a reaction increases the number of gas molecules, the standard state
entropy
increases as gases have higher entropies than
solids or liquids
δG θ = ΔH θ T δsθ
Simpler substances with fewer atoms have lower entropy
values than
more complex substances
For similar substances, harder substances have lower
entropy values
Predicting spontaneity:
‎∆G State of Reaction Stability of Compound
13.3. Entropy Change in Exo/Endo
-ve Spontaneous More stable
Reactions +ve Not Spontaneous Less stable
0 Equilibrium -
Exothermic Reactions Endothermic Reactions
Energy released to Energy absorbed from
surroundings surroundings 13.7. Gibbs Free Energy Calculations
Increases ways of arranging
Decreases ways of arranging ‎
the energy of molecules in
the energy
surrounding
Entropy increases Entropy decreases
Increased probability of Increased probability of
chemical change occurring chemical change occurring
spontaneously spontaneously

13.4. Calculating Total Entropy Change

Firstly, calculate the entropy change for a reaction ΔG θreaction = ΔG θ2 − ΔG θ1
​ ​ ​

ΔS θ system = ΔS θ products −ΔS θ reactants

Next, calculate entropy change in the surroundings Form Hess’s cycle and calculate Free Energy as you would
θ
−ΔHreaction enthalpies
(using moles etc.)
ΔSsurroundings
θ =
​

T ​

T in Kelvin; std. temp. = 298K 13.8. Enthalpy and Entropy Driven

θ
If ΔHreactionin kJ
mol-1, change to J by × 1000
Enthalpy-driven reaction: flow of thermal
​

Negative sign part of equation, always put it

If ‎∆H > T∆S energy provides most of the free energy in
Use values calculated to find total entropy change the reaction
ΔS θ total = ΔS θ system −ΔS θ surroundings Entropy-driven reaction: increased disorder
If ‎∆H < T∆S provides most of the free energy in the
θ
If ΔStotal positive, reaction
is feasible
​

reaction

13.5. Entropy in Equilibrium Reactions

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13.9. Temperature Change & Reaction carried out

again by rotating the chromatogram 90o and
re-running in
a different solvent
Spontaneity
For exothermic reaction:
if temperature is increased
T ΔS value becomes more +ve
ΔG +ve ∴ less likely to be
spontaneous
For endothermic reaction:
if temperature is increased 14.3. Thin Layer Chromatography
T ΔS value become more -ve
ΔG -ve ∴ more likely to be
spontaneous As solute rises with solvent, they get separated from
mobile phase
and adsorbed to the stationary phase
Adsorption: separation due to different attraction
14. Analytical Techniques between the
compound and the stationary phase, relative
to their solubility in
the solvent
The solid in stationary phase is either Al2O3
or SiO2; it is
14.1. Paper Chromatography
spread onto a microscope slide as a slurry
using water
and then dried into a white coating
Polar molecules have a greater attraction for a polar solid
used as
stationary phase and they are adsorbed more
strongly onto its
surface ∴ travel more slowly
If dried silica or Al2O3 become rehydrated,
water also acts
as a partitioning stationary phase together with the
adsorbing stationary solid phase
Mobile phase: solvent in the chromatography process,
TLC is quicker than paper chromatography and can be
which moves
through the paper or thin layer
Stationary phase: immobile phase in chromatography that used on smaller
samples
For colourless spots:
the
mobile phase passes over or through
Keep plate in closed container with I2 crystals.
I2 vapor
As the solute rises with the solvent, they get separated by
partition from mobile phase to the stationary phase accumulate on spots which appear dark brown
Place plate under UV light; the glow is reduced by
Depending on solubility, the solutes migrate at different solutes which
appear as dark spots on the bright plate
rates and
travel up to different distances
Partition: separation due to different solubilities of 14.4. Gas/Liquid Chromatography
compound
in two solvents
The more polar a solute component is, the less it travels Used to separate and identify very small samples of
as there
are stronger H-bonds to H2O of st. phase gases, liquid
and volatile solids
Identifying components:
Compare position/colour on filter paper with those of
known pure
compounds
Find and compare the Rf value
Rf value: ratio of the distance a component has
travelled
compared with distance travelled by the solvent front
When using Rf values to identify a substance, conditions
in The vaporized sample is carried by an inert gas (mobile
which chromatography is carried out must be identical to phase) over
the surface of a liquid (stationary phase)
those
quoted in Rf data table (e.g. temp, solvent) When stationary phase is non-polar, rate of movement is
determined principally by volatility
Distance Moved by Solute Spot
Rf = When stationary phase is polar, it will tend to retain polar
Distance Moved by Solvent Front
​ ​

components of the mixture

Colourless chromatograms can be seen by spraying a Components of a mixture leave the column after definite
locating agent
(e.g. ninhydrin) to reveal spots intervals of
time and are monitored by a detector
designed to record changes in
composition of carrier gas
Retention time: time it takes components to reach the
14.2. Two-way Chromatography detector
from time of injection
Determination of % composition of a mixture by GLC:
When two or more components in a mixture have similar
Peaks are roughly triangular in shape so area is:
Rf
values in a particular solvent, chromatography can be

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1 Percentage abundance of Cl and Br isotopes

× base × height
2
​

Isotope Approx. % Isotope Approx. %

‎
35Cl 75% 79Br 50%
37Cl 25% 81Br 50%

14.7. Proton (1H) NMR Spectroscopy

Peak Area of X
e.g. % of X
= Sum of Areas of X and Y ​

Technique Separation Method

Paper chromatography Partition
Thin-layer chromatography Adsorption
Gas/liquid chromatography Partition

14.5. Mass Spectrometry

The mass spectrometer:

The hydrogen nucleus behaves as a tiny magnet.

These "magnets" can align themselves with or against an
applied
magnetic field
A vaporized sample is injected through the vapor inlet There is an energy gap between these two alignments,
The sample is ionized to form positive ions which
corresponds to the energy in radio frequencies.
The positive ions are accelerated by an electric field The size of energy gap between the two alignments
Accelerated positive ions are deflected by magnetic field depends on the
other atoms in the molecule around it –
Positive ions of a particular mass/charge ratio are molecular environment
detected –
recorded as a series of peaks: mass spectrum TMS, Si(CH3) 4 is used as standard because:
It is an inert volatile liquid
Molecular ion (M+): the peak at the highest mass to
Most organic compounds are soluble in it
charge ratio; gives relative molecular mass of sample
Contains 12 H atoms in the same environment which
Base peak: peak in a mass spectrum that corresponds to
produces a
single, strong peak
the most
abundant fragment
NMR must be carried out in solution
During bombardment, some energy is transferred to the
CCl4 can be used as a solvent as it has no H & inert
ion, weakening
the bonds and breaking molecular ion into
CDCl3 (deuterated solvents) can also be used because
fragment +ve ions &
radicals; only +ve ions detected
Fragmentation: the breaking up of a molecule into smaller signal produced by D does not lie in spectrum area of
parts
by the breaking of covalent bonds H
The horizontal scale of magnetic field is measured in units
called
chemical shift δ (ppm)
14.6. Applications of Mass TMS is considered as 0 and all other compounds are
Spectrometry compared by
quoting shift away from TMS line
Low Resolution NMR:
Finding number of carbon atoms using M and [M+1] peak Shows single peaks for each non-equivalent H-atoms
Relative peak areas proportional to no. of H-atoms
[M+1] peak: an ion that has a mass one unit greater than Can use shift value to identify type of H-atom present
the
molecular ion in a mass spectrum, due to presence of High Resolution NMR:
the
13C isotope The NMR signal is also affected by magnetic field of H-
atoms on
neighbouring C atoms
100 abundance of [M + 1]+ ion Causes peaks to split in particular patterns due to
n= ×
1.1 abundance of M +  ion spin-spin
splitting
​ ​

Identifying Cl and Br using [M+2] and [M+4] peaks

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14.8. (n + 1) Rule No. of Chemical Type of Splitting No. of H on

H shift proton pattern adj. C
n hydrogens on an adjacent carbon atom will split a peak 6 3.30 -O-CH3 Singlet 0
into
n + 1 smaller peaks 1 4.60 -O-CHR2 Quartet 3

No. of Adjacent 1H Splitting Ratio of Peak Final molecule: (CH3O) 2CH-CH3

atoms Pattern Heights

14.11. Carbon-13 NMR Spectroscopy

1 peak
0
Singlet ‎ Although C-12 does not produce NMR signals as it has an
1 even no. of
protons, approximately 1.1% of an organic
compound would have C-13
which produces a signal
2 peaks
1 ‎ C-13 NMR produces a spectrum with different chemical
Doublet
1:1 shifts for
non-equivalent carbon atoms in a molecule
Signals produced are discrete vertical lines on the spectra
3 peaks (no
splitting)
2 ‎
Triplet The heights of the lines are not usually proportional to no.
1:2:1
4 peaks ‎ of
13C atoms present
3 The solvent used for analysis is CDCl3 that produces a
Quartet 1:3:3:1
small signal at 80ppm which can be ignored
of hydrogens
attached to the carbon atom next door Use chemical shift values as in proton spectroscopy to
identify
protons present & hence work out the molecule

14.9. Identifying –OH or –NH Signal

15. Organic Synthesis
The –OH signal always appears as a single peak because
the H atom is
exchanged rapidly with those in water
causing it to appear
unaffected to spin-spin splitting 15.1. Chiral Drugs from Natural Sources
ROH + H2O $\rightleftharpoons$ RO + H3O Most chiral drugs extracted from natural sources often
contain only
a single optical isomer.
Deuterium is an isotope of hydrogen that behaves In biological systems, molecules are synthesized and
chemically like H
but different magnetic properties to H so broken down by
reactions involving enzymes
don't produce peaks in the
area of spectrum with H These reactions work by a lock-and-key mechanism and a
Organic compounds are shaken with deuterium oxide molecule has
to be the right shape to fit the enzyme
(D2O)
and the H-atoms bonded to electronegative atoms Different arrangements around a chiral center will force
(–OH and –NH) are
replaced; deuterium exchange an entirely
different shape on the molecule, and it may no
longer fit the enzyme
ROH + D2O $\rightarrow$ ROD +DHO So enzyme systems will tend to produce a single optical
When this is done, the NMR signal due to –OH and –NH isomer
because that is the only shape, they work with
hydrogen
disappears, confirming that the peaks were caused
by those groups
15.2. Synthesis of Chiral Drug Molecules
14.10. Describing an NMR Spectra Each chiral center will have two possible arrangements of
bonds
around it and a different arrangement of bonds will
For example: mean a
differently shaped molecule
Differently shaped molecules won't necessarily fit the
active site
of an enzyme, and hence wouldn’t function
e.g. one enantiomer of a drug used to treat tuberculosis is
effective while the other can cause blindness
Using pure enantiomers will be beneficial as it:
Reduces patient’s dosage by half as pure enantiomer
To identify the protons present, set up a table as follows is more
potent; better therapeutic activity
Minimizes risk of side effects thereby protecting
No. of Chemical Type of Splitting No. of H on patients from
further problems
H shift proton pattern adj. C Reduces cost of production because all that is
3 1.30 -CH3 Doublet 1 produced can be
used as the drug

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Producing pure enantiomers:

Optical resolution: the drug is produced following
traditional synthesis route and then a single
enantiomer is
separated physically by adding a
substance that reacts with the
other isomer
Optically active starting material: drug produced from
optically active starting material (e.g. carbohydrates
or
amino-acids) with the same orientation as desired
and then
synthesize drug, keeping enantiomer the
same
Chiral catalysts: using enzymes from living things or
synthetic enzymes, the drug can be produced and only
one
enantiomer is formed because enzymes have
specific active sites
that can only produce one type
Trying to produce just one isomer is known as asymmetric
synthesis
(the last 2 methods)

16. Partition Coefficient

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