ZNOTES.

ORG

UPDATED TO 2022 SYLLABUS

CAIE A2 LEVEL
CHEMISTRY (9701)
SUMMARIZED NOTES ON THE THEORY 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
(ΔHθat ): 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  2nd  and 3rd
​

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
(ΔHθlat ):
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
(ΔHθsol ):
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
(ΔHθhyd ):
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 (ΔHθea ): 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 more –ve = more
soluble
conditions
e.g: Cl (g) + e- → Cl- (g) 1.7. Ion Polarization
1st electron affinity is exothermic
2nd, 3rd… electron affinities are endothermic
because Ion polarization: distortion of the electron cloud on an
when electron added to –ve ion, increased repulsion anion
by a neighbouring cation
present
therefore requires input of energy

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CAIE A2 LEVEL CHEMISTRY (9701)

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
‎
Mg2+ > 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+ > Mg2+ 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 lat also decreases but

decrease is relatively smaller
θ
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 Following results from

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

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

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CAIE A2 LEVEL CHEMISTRY (9701)

1 faraday (F): quantity of electric charge carried by 1 mol

of
electrons = 96,500 C
Relationship: F = Le
F = Faraday’s Constant
L = Avagadro’s Constant
e = charge on 1 electron ‎
Example:
To liberate 1 mol of H2(g)

2H+(aq) + 2e­-→ H2(g)

 ∴ requires 2 faradays of electricity to form 1 mole­

2.4. Standard Electrode Potentials Eθcell = EθRed - EθOx

Eθcell ‎= 0.34 - -0.76 = 1.10‎
Standard electrode (redox) potential
Eθ : the electrode
potential of a
half cell measured under standard
conditions using a standard
hydrogen electrode as the 2.6. Salt Bridge
other half cell
Standard cell potential
Ecell : the
difference in standard
θ ​
Used to complete the electrical circuit allowing the
electrode potential between two half cells movement of
ions between two half cells so that ionic
Standard conditions: balance is maintained;
electrically neutral
Temperature: 298 K A strip of filter paper soaked in KNO3(aq)
Pressure: 1 atm (101 kPa) Salt used should not react with ions forming a ppt. e.g.
Concentration: 1.00 mol dm-3 KCl in a
cell containing Ag2+ would form insoluble ppt.

2.5. Electrochemical Cell 2.7. Standard Hydrogen Electrode

(S.H.E.)
It is a reference cell, used to measure E θ of any other
half
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
ANODE CATHODE mol dm-3 conc. (e.g. HCl­(aq) or ½
H2SO4(aq))
-ve electrode/half cell +ve electrode/half cell Pt electrode is inert, allows conduction and is coated with
finely
divided Pt serving as a catalyst. Being porous,
Eθ of half-cell is more -ve (less Eθ of half-cell is more +ve
retains large
amounts of H2(g)
+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)

‎
The more –ve (less +ve) the The more +ve (less -ve) the
Eθ, the more easily it gets Eθ, the more easily it gets 2.8. Measuring Eθ of a Half Cell using
oxidized ∴ stronger reducing reduced ∴ ‎ ‎stronger oxidizing
agent agent S.H.E.
Metals in contact with their aq. solution

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CAIE A2 LEVEL CHEMISTRY (9701)

Reaction Eθ
Cl2 + 2e-→ 2Cl- +1.36

Br2 + 2e-→ 2Br- +1.07

I2 + 2e- → 2I- +0.54

Non-metals in contact with their aq. solution
2.11. Concentration of aq. Ions

Fe3+ + e- ⇌
Fe2+­ E θ = 0.77V

If F e3+ increased or F e2+ decreased,

equi. favours
Pairs of ions with different oxidation states forward reaction ∴ E becomes more +ve
(0.85V)
If F e2+ increased or F e3+ decreased,
equi. favours
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
2.9. Feasibility of a Reaction values can change
greatly

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

Ecell
θ must be
​

2.12. Nernst Equation

positive
Equation relating voltage of chemical cell to its standard
Finding whether a reaction is feasible:Will chlorine oxidize potential
and to concentrations of reactants & products
F e2+  ions to Fe^{3+}$ ions?
SolutionIdentify which is the R.A./O.A. from RT [oxidized form]
E = Eθ + ln  
questionChlorine is the O.A therefore is reducedIdentify zF [reduced f orm]
​ ​

relevant equations from data booklet and place in correct

z is number of electrons transferred in reaction
direction. If using opposite direction, switch sign for value of
Eθ F is the value of the Faraday constant 96,500 C
mol-1 
Cl2 + 2e− → Cl−
​

Simplified relationship by substituting standard values

E θ = +1.36
0.059 [oxidised form]
F e2+ → F e3+ + e− E = Eθ + log  
[reduced f orm]
​ ​

z
θ
E = − (+0.77)
Add Eθs together. If positive, reaction occurs and is feasible If conc. less than 1 mol dm-3,
log [oxidized f orm] is –ve
otherwise, does not occur spontaneously. and E is less
than E θ

1.36 − 0.77 = 0.59 If conc. more than 1 mol dm-3,

log [oxidized f orm] is
Reaction occurs spontaneously and is feasible +ve and E is more
than E θ

2.10. Oxidizing Ability of Halogens (Gp. 2.13. Hydrogen Fuel Cell

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
ordering them
in descending order of E θ , most reactive
Consists of:
to least
Two platinum coated porous electrodes that allow
Reaction Eθ gases to pass
through
Electrolyte; either acidic or alkaline
F2 + 2e-→ 2F- +2.87

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CAIE A2 LEVEL CHEMISTRY (9701)

  Strong Acids Weak Acids

Acidic electrolyte:
HA(aq) + H2O(l) ‎→‎H+(aq) + A- HA(aq) + H2O(l) ‎⇌‎H+(aq) + A-
-ve Electrode (anode): (aq) (aq)
Eq. position to the right Eq. position to the left
2H2(g) 4H+(aq) + 4e- Dissociates completely ∴‎‎ Dissociates partially ‎∴‎
\[Acid\] = \[Ions\] \[Acid\] ≠
‎ ‎\[Ions\]
+ve Electrode (cathode):
[H + ] [A− ]
O2(g) + 4H+(aq) + 4e-
2H2O(l)
Kc =
[HA] [H2 O]
​ ​

Overall reaction:

Water dissociates very slightly; conc. remains constant ∴

O2 + 2H2(g) 2H2O(l) can eliminate from equation

H+ ions removed at +ve electrode replaced by those [H + ] [A− ]

produced at –ve electrode so conc. of electrolyte remains Ka =
[HA]
​ ​

constant

 
Alkaline electrolyte: 3.2. pH Scale
-ve Electrode (anode): Gives strength of acid depending on

2H2(g) + 4OH-(aq)
4H2O(l) + 4e- H+

+ve Electrode (cathode): Use – log of values as they are very small giving pH
Lower pH value, stronger the acid
O2(g) + 2H2O(l) + 4e-
4OH-(aq)
− log [H + ] = pH ⇔
[H + ] = 10−pH
Overall reaction: Calculating pH of a strong acid:
Find the pH of 3.6 × 10-5 mol dm-3
HNO3
O2 + 2H2(g) 2H2O(l)
Solution
It is a strong acid and dissociates completely the conc. of ions
OH- ions removed at -ve electrode replaced by those is
equal to conc. of the acid
produced at +ve electrode so conc. of electrolyte remains
constant [H + ] = [HNO3 ] = 3.6 × 10−5 ​

  Calculate the pH by logging the conc.

Advantages:
pH = − log (3.6 × 10−5 ) = 4.44
No pollutants – by product is water
More energy per gram of fuel than other fuels
Lightweight
3.3. Ionic Product of Water, Kw
Operate with high efficiency
Water molecules can function as both acids and bases;
one molecule
(base) accepts H+ from second one (acid)
3. Equilibria
H2O(l) ⇌
H+(aq) + OH-(aq)
3.1. Behaviour of Acids and Alkali [H + ] [OH− ]
Kc =
[H2 O]
​ ​

When acids and alkalis are added to water, they ​

dissociate/ionize and a dynamic equilibrium is set up

Conc. of water remains constant ∴ can eliminate from
General equilibrium of an acid (can be simplified to H+) equation and find the ionic product of water, Kw

Strong Acids Weak Acids Kw = [H + ] [OH− ]

​

At 25oC, the Kw of water is 1.00 x

10-14 mol2 dm-6
− log throughout equation,
− log 1 × 10−14 = 14 ∴

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CAIE A2 LEVEL CHEMISTRY (9701)

14 = pH + pOH Reduces H+ Increases H+

pH of an alkali can be calculated using this formula pH of blood unchanged

 
3.7. Calculating pH of Buffer Solutions
Calculating pH of a strong base:
Calculate the pH of a solution of sodium hydroxide of [Salt]
concentration
0.05 mol dm-3 pH = pKa + log ( )
[Acid]
​ ​

Solution
It is a strong base and dissociates completely the conc. of Calculating pH of buffer solution:
ions is
equal to conc. of the solution A buffer solution is made by adding 3.28g of CH3COONa to 1
dm3 of 0.01 mol dm-3 CH3COOH
[OH − ] = [NaOH] = 0.05
Calculate pOH by logging
1. What is the pH of this buffer (Ka
= 1.8 ×  10−5 )

pOH = − log 0.05 = 1.30 What is the change in pH when 1 cm3 of 1 mol
dm-3 NaOH is
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
pH = 14 − pOH = 14 − 1.30 = 12.7 Moles

Mass 3.28
3.4. Buffer Solutions = = = 0.04
Molar Mass 82
​ ​

Buffer solution: a solution in which pH doesn’t change Concentration

significantly when small amounts of acids or alkali added Moles 0.04
A buffer solution can be: = = = 0.04
Volume 1
​ ​

Acid: Weak acid + its salt

e.g. CH3COH and CH3COONa Use formula to calculate pH:
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):
HA(aq) ⇌
H+(aq) + A-(aq) &
MA(aq) → M+(aq) +
A-(aq) NaOH reacts with acid:
NaOH(aq) + CH3COOH(aq)
CH3COONa(aq) + H2O

3.5. Working of an Acid Buffer Calculate no. of moles of NaOH used:

Moles

= Concentration ×  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
CO2(aq) + H2O(aq)
⇌ H+(aq) +
HCO3-(aq) = = 0.0410
1  +  (1 ×  10−3 )
​

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:

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CAIE A2 LEVEL CHEMISTRY (9701)

ΔpH = 5.40 − 5.35 = 0.05 2F-(aq)

Calculating pH of buffer solution with different volumes of Write down the equilibrium expression
acid and
salts:
What is the pH of the buffer solution formed when 40cm3 of Ksp = [M g 2+ ][2F − ]2
​

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

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

2
HNO2(aq) + NaOH(aq) NaNO2(aq) +
H2O(l) 10−3 ) × 2 × (1.22 × 102 )
Calculate the moles of each reactant
Ksp = 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 1 Will a ppt. BaCO3 (Ksp = 8.1 × 10−9 )
form from solution
0.06 = 3
​ ​

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 = 0.1

​

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:
Fe2S3(s) ⇌
2Fe3+(aq) + 3S2-(aq) BaSO4 is a sparingly soluble salt (Ksp
= 1.0 × 10−10 mol2
Ksp =
2Fe3+23S2-3
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 SO4 ] = [SO42− ] = 0.1
​

​ ​ ​

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Use new conc. of SO42- and ignore original as it

is negligible When solute added to two immiscible solvents, a dynamic
to calculate new Ba2+ equilibrium
is set up where particles move between the
two solvents but
concentration in each remains constant.
Ksp 1.0 × 10−10 Hence, can calculate a constant k for the equilibrium
[Ba2+ ] = 2− = = 1.0 × 10−9
​

[SO4 ] 0.1 Partition coefficient (Kpc): equilibrium constant

that
​ ​

relates the concentration of solute partition between two

Hence, solubility has decrease by a factor of 10−4 immiscible solves at a particular temperature.

Conc. of  Solute in Solvent 1
3.11. Titration Curves Kpc =
​

Conc. of  Solute in Solvent 2
​

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

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CAIE A2 LEVEL CHEMISTRY (9701)

6.0×10−4
conc. of NH∗3(org) 50×10−3 Half-life,
K pc = = Order Graph of
​

conc. of NH∗3(aq) 9.4×10−3
t1/2
​ ​

100×10−3
​

‎ ‎
Kpc = 0.1277
​

3.14. Working of an Alkali Buffer ‎[A]0 ‎ Decreases

‎ ‎

[A]1 Constant

‎ ‎

4. Reaction Kinetics
[A]2 ‎ Increases
4.1. Rate of Reaction
Rate of reaction is the change in concentration of
products/reactants per unit time

[   ] For zero order, rate of reaction not dependant on conc. of

R= t ​                        Unit: mol dm-3 s-1 that
reactant but it is need for completion of reaction.
Reaction
continues until all of that reactant is used up.
4.2. Rate Equation Recognize shapes above in graphs given to work out
order of reactant
and construct rate equation. Calculate k
Rate equations: states the relationship between the rate using data from
graph(s).
constant and the concentrations of those reactants
Constructing rate equation using conc. data:
xA  +  yB → P roducts Using following data from the experiments construct a rate
equation
and calculate rate constant.
m n
R = k [A] [B]
Rate constant (k): proportionality constant in
rate eqn.
Larger the rate constant, faster the reaction
Solution
Depends on temperature
Use data and deduce orders by looking at changes in conc.
Unit depends on overall order of reaction
and rates
(arrows added above):
Order of reaction (m, n): power to which conc.
of the
Order of A = 1                           Order of B = 1
reactant is raised in experimentally determined rate eqn.
Write as rate equation
Overall order of reaction = m+n
R = k [A] [B]
Half-life, t 1 of a
reaction is the time taken for conc. of
Calculate* k *using data given from e.g. experiment 1
​

2
​

one of the reactants to fall

by half
R 4.0 × 10−4 1
k= = =
4.3. Order of Reaction [A] [B] 0.040 × 0.030 3
​ ​ ​

1
Order
Half-life,
Graph of
∴R= [A] [B ]
3
​

t1/2
Conc./Time Rate/Conc.
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 ][F2 ]
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 C4H9Br + OH-
C4H9OH + 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: Measure change in volume of gas using a gas syringe
slow Take down readings at regular intervals
C3 H7 C H 2 B r  +  OH −
​ ​ ​ ​ [C3 H7 B rOH]
​ ​

Plot graph and calculate rate of reaction

f ast
[C3 H7 B rOH]
​ ​ ​ C3 H7 C H2 OH + Br−
​ ​ ​
Changes in Colour:

∴ k[C3 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
(CH3 )3 CBr ​ ​ ​ (CH3 )C +   +  Br− ​
Colorimeter measures amount of light absorbed as it
passes through
solution; recorded as absorbance.
f ast
(CH3 )C +   +  OH −
​ ​ (CH3 )COH  +  Br− ​

∴ R = k[(CH3 )3 CBr] ​ ​

 
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
Adsorption;
S2O82- + 2I- $\xrightarrow{slow}$
2SO42- + I2
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
S2O82- ions enough to
weaken
S2O82- + 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
Diffusion of
with
catalyst
NH3 away
Molecular rearrangement occurs - bonds in reactants
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 dxy , dxz and dyz have
d-orbitals in between axis
​ ​ ​

more
stable ions with incomplete d orbitals dx2 −y2 and dz2 have d-orbitals along
axis
​ ​

dz2 is formed by the merging of dx2 −z2

and dy2 −z2
​ ​ ​

5.2. Electronic Configurations

5.4. Physical Properties
Element Electronic Config. Oxidation States
Sc, scandium [Ar] 3d1 4s2 +3
Ti, titanium [Ar] 3d2 4s2 +3, +4
V, vanadium [Ar] 3d3 4s2 +2, +3, +4, +5
Cr, chromium [Ar] 3d5 4s1 +3, +6
Mn, manganese [Ar] 3d5 4s2 +2, +4, +6, +7
Fe, iron [Ar] 3d6 4s2 +2, +3
Co, cobalt [Ar] 3d7 4s2 +2, +3
Ni, nickel [Ar] 3d8 4s2 +2
Cu, copper [Ar] 3d10 4s1 +1, +2
Zn, zinc [Ar] 3d10 4s2 +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
atom/ion surrounded by one or more ligands
ligand
A complex consists of:
If ligands all neutral/-ve or contain more than one of
Central transition metal ion (+ve) that can accept
e-s each,
name in alphabetical order
Ligand (-ve): a species that contains a lone pair of
e-s
that forms a dative bond to a central metal
atom/ion Anions Neutral Ligands
Coordination no.: number of coordinate or dative bonds Amine (NH3)
Fluoro (F-), Chloro (Cl-)
to the
central metal atom/ion
Different metal ions show different coordination number Cyano (CN-) Aqua (H2O)
with same
ligands Hydroxo (OH-)
Transition metals form complexes because
Ion are small in size so they have a strong electric field Name central metal ion
around them which attract e--rich ligands If complex ion +ve/neutral – use normal name
They have empty 4s and 4p orbitals that are If complex ion –ve, use name ending –ate; special:
hybridised and can
accept e- Iron = Ferrate
Lead = Plumbate
Copper = Cuprate
5.7. Ligands
Oxidation no. of metal ion in Roman numeral and ‘ion’
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-
Cyanide CN-
5.9. Writing Formulae of Complexes
Thiocyanate SCN- Metal ion written first followed by ligand
Place charge on formula in square brackets
Bidentate ligands: forms 2 coordinate bonds with central Total charge on complex = sum of charge on metal
metal
ion (donates 2 pairs of e-s per molecule) ions and charge
on ligand
If ligands all neutral, charge on complex = charge on
metal ion

5.10. Shapes of Complexes

‎

H2N – CH2 – CH2 – NH2 -O Coordination No.

– CO – CO – O-
Diagram
& Shape
Ethylene diamine (en) Oxalate ion
(neutral) (oxalato-)
6
png" width=20%>

Octahedral

Forms 6 coordinate bonds \[Fe(H2O)6\]2+

4 from oxygen
2 from nitrogen
4
5.8. Writing Names of Complexes

Tetrahedral

To represent coordination number \[CoCl4\]2-

For monodentate ligands, use prefixes mono-, di-, tri-, 4

tetra-,
hexa-

Square Planar

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(most Ni and Pt) 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- >
S2O32- > 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
H2O [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
NH3 (excess) [Cu(NH3)4(H2O)2]2+ [Co(NH3)6]2+ constituent ions or molecules
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− ]

Kstab =
​

2+ 4
[Cl− ]
​ ​

Reaction with Hydroxide Ions

[[Cu(H2 O)6 ]
​ ​

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 log10 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 dx2 −y2 and dz 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 (sp2 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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Regenerating catalyst:
6.4. Electrophilic Substitution
2HSO4- + H3O+ +
H+→ 2H2SO4 + H2O
Mechanism
Alkylation / Acylation
An H-atom on the ring can be substituted by other
AlCl3
atoms/groups C6H6(l) + RCl/RCOCl
C6H5R/C6H5RCO +
HCl(g)
​

All carbon atoms identical and benzene ring symmetrical Reagent:

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

6.6. Electrophilic Addition Reaction

Hydrogenation
N ickel
C6H6(l) + 3H2(g)
C6H12
​

E+ attacks π e- ring, accepting a pair

of e- from benzene Type of reaction:
An intermediate +ve specie is formed in which +ve charge electrophilic addition
is
delocalized around the ring (more stable than a normal Conditions:
carbocation) Temp.: 150ºC
Proton eliminated from +ve intermediate to restore Catalyst: nickel
stability and
π system of delocalized e-s reformed
6.7. Side Chain Reactions
6.5. Electrophilic Substitution Reactions
Chloromethyl Benzene
Halogenation
C6H5CH3(l) + Cl2(g) →
C6H5CH2Cl(l) + HCl
catalyst Type of reaction:
C6H6(l) + X2(g/l)
C6H5X(l) + HX(g)
free radical substitution
​

Reagent:
Reagent:
dry Cl2 gas / pure Br2 liquid
Cl2(g)
Conditions:
Condition:
Temp./press.: r.t.p.
u.v. light
Catalyst: anhydrous AlCl3(s) / FeBr3(s)
With excess Cl2 a mixture of di, tri chloromethyl benzene
Generating electrophile:
can be obtained
catalysts are e- deficient halogen carriers, form
dative
bond drawing e- from halogen molecule
producing X+  
Benzoic Acid
AlCl3 + Cl2 → [AlCl4]- +
Cl+
Regenerating catalyst: C6H5CH3(l) + 3[O] →
C6H5COOH(l) + 2H2O
H+ + −
[AICl4 ] → HCl + AlCl3
​ Type of reaction:
oxidation
Nitration Reagent:
KMnO4(aq) or
K2Cr2O7(aq)
C6H6(l) +
H2SO4/HNO3 →
C6H5NO2(l) +
H2SO4(g) + H2O
Condition:
Reagent:
heat under reflux (2 to 3 hours)
nitrating mixture
Alkyl gp. always oxidized regardless of chain length
conc. HNO3 / conc. H2SO4
If more than one alkyl gp., each one oxidized
Condition:
Temp.: 45-55oC under reflux
6.8. Ring Activating/Deactivating
Generating electrophile:
2H2SO4 + HNO3 → 2HSO4- + NO2+ + H3O+ Groups

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

8.2. Solubility and Acidity of Phenol

7. Haloarenes
7.1. Reactivity of Benzene & ‎
Chlorobenzene
OH group forms H-bonds with water molecules however
there are weak
VDW forces due to heavy nonpolar
Chlorobenzene is less reactive than benzene because:
benzene ring hence phenol partially
soluble in water
Chlorine is a ring deactivating group Solution of phenol is slightly acidic because –OH in
Chlorine is more electronegative than carbon, and draws phenol breaks
to form H+
electrons in
the ring towards itself. Bond breaks readily because phenoxide ion formed is
Hence electron density around ring decreases, less stabilized by
partial delocalization of –ve charge over the
attractive for
electrophiles and so reaction is slower 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
react
with H+ going back to phenol
Lone pair of e‑s of Cl overlap slightly with p
orbitals of
benzene ring giving C–Cl a double bond character
8.3. Acid-Base Reactions
Makes C–X bond much stronger therefore nucleophilic
substitution
difficult
Reaction with Base
High density of e-s on benzene ring tends to repel the
r.t.p
approaching –ve charged nucleophile. C6H5OH(l) + NaOH(aq)

C6H5O-Na+(aq)
​

H2O
7.3. Nucleophilic Substitution Reaction Type of reaction:
Neutralization
Hydrolysis Reagent:
sodium hydroxide
C6H5Cl(l) + NaOH(aq)
→ C6H5OH(l) +
NaCl(aq) Condition:
Type of reaction: r.t.p.
nucleophilic substitution Regenerating phenol:
Reagent: When strong acid (HCl) added to solution of sodium
sodium hydroxide phenoxide,
phenol regenerated
Condition:
C6H5O-Na+(aq) + HCl(aq)­ →
C6H5OH(l) + NaCl
Temp.: 300-330oC Initially dense white emulsion formed then slowly oily
Press.: 150-300 atm liquid
layer of phenol separates
Rate of Hydrolysis: (slowest to fastest)

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8.5. Relative Acidities
Reaction with Sodium
r.t.p
C6H5OH(l) + Na(s)
C6H5O-Na+(aq) + ½H2(g)
​

Type of reaction:
metal and acid, redox
‎
Condition:
r.t.p. The stronger the acid:
Reacts with Na liberating H2 gas Higher the Ka value
Note: phenol does not react with metal carbonate to
More easily H+ is donated
liberate
CO2 hence shows its fairly weaker than other
More stable is the conjugate base
carboxylic
acids
 
8.4. Reaction with Benzene Ring Ethanol: C2H­5OH + H2O
⇌ C2H5O- +
H3O+

Ka: 10-18 mol

dm-3
Ability to donate H+ ions:
C2H5 is an e- donating gp.
which increases charge
density on O of OH

Bromination ‎

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

Stability of conjugate base:

Type of reaction: In ethoxide ion, C2H5 gp. increases –ve
charge
electrophilic substitution Makes ethoxide ion more basic than OH-
Reagent:
Ability to accept H+ increases, moving equi. to left
aq. Bromine
Condition:
r.t.p. (no catalyst) ‎
Rapid reaction, forms a white ppt.  
No catalyst needed since Br2 molecule easily polarized by
Water: H2O + H2O ⇌
OH- + H3O+
increase e-
­ density in ring
Ka: 10-16 mol
dm-3
 
No e- donating or withdrawing gp. present hence ability
Nitration
to donate and accept H+ ion is the same

 
Type of reaction: Phenol: C6H­5OH + H2O
⇌ C6H5O- +
H3O+
electrophilic substitution
Reagent: Ka: 10-10 mol
dm-3
dilute nitric acid Ability to donate H+ ions:
Condition:
OH is a ring activating gp. & the lone pair of e-s on
O
r.t.p.
If concentrated nitric acid used, then trinitrophenol becomes part of delocalized e- system
produced Decreases e- density on O of OH and attraction
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

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

These are derivatives of carboxylic acids; -OH gp. of acid 9.4. Nucleophilic Condensation
replaced
by Cl
Named after corresponding acid using suffix –oyl Reactions
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 acid from
which they are derived R—CO—Cl + HO–R → R–CO–OR(aq) + HCl(aq)
Polarity of both C=O and C—Cl bond produces relatively Reagent & Condition:
large
δ + charge on the carbon, making it e- deficient
and Aliphatic alcohol at r.t.p
more susceptible to attack by a nucleophile Phenol dissolved in NaOH, warm it
Hydrolysis of esters:

9.5. Relative Ease of Hydrolysis

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−Increasing ease of hydrolysis→ Chlorine atoms show a –ve inductive effect withdrawing –
Alkyl ve charge
from the molecule, reducing the strength of the
Aryl Chlorides Acyl Chlorides
Chlorides O–H, and hence
making H+ be lost more easily
Conjugate base is more stabilized due to the extended
R–Cl
‎ delocalization
of the negative charge on the –COO- and so
less likely to
bond with a H+ ion
Aryl chlorides do not undergo hydrolysis at r.t.p because
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 If an e- withdrawing gp. present molecule more acidic
r.t.p
because the carbon atom is bonded to two highly
electronegative
atoms hence has a high δ + therefore
10.4. Oxidation of Carboxylic Acids
attack by a nucleophile
is much more rapid
Acid + Oxidizing Agent (warm) $\rightarrow$ CO2 + H2O
10. Carboxylic Acids Methanoic Acid

HCOOH + [O] → CO2 + H2O

Carboxylic acids are weak acids and dissociate With Tollens’ Reagent:
incompletely in
aqueous solutions
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  

Ethanedioic Acid
carbonyl group
C=O
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

11. Nitrogen Compounds
Acids
Primary Amine Secondary Amine Tertiary Amine
Acidity of carboxylic acids decreases as carbon chain length
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+
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 11.2. Formation of Alkyl Amines

Substitution
Acidity of carboxylic acids increases when H atoms are
substituted by
electro-ve (withdrawing) atoms e.g. Cl R–X + NH3 → R–NH2 + HX(g)
Type of reaction:

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

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

11.4. Basicity of Amines

Bases are proton acceptors (electron donors)
N-atoms in amines have a lone pair of e-s (–N2+ is called diazonium ion)
N donates lone pair and accepts H+ forming dative bond
Type of reaction:
diazotization reaction
Reagent:
nitrous acid (NaNO2 with excess HCl(aq))
(HNO2 weak, unstable acid so produced by reaction
NaNO2 with excess HCl)
Condition:
low temp. (5∘ C)
11.5. Relative Basicity Note:
Diazonium salts of aryl amine stabilized by
‎
delocalization of
–N2+ ion’s e-s over benzene
ring
However, diazonium ion highly unstable and can
decompose above
10oC to

Phenyl amine weaker Ammonia Ethylamine stronger

than ammonia than ammonia

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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:
‎ 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
ethanoyl chloride + methyl amine → N-methyl soluble in water
methanamide
11.13. Amino Acids in Acidic/Basic
11.9. Neutrality of Amides Conditions
The presence of the electron withdrawing oxygen atom
means that the
lone pair on the amide’s nitrogen atom is

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If acid added, the –COO- part of the zwitterion accepts

an Factors that Determine the
H+ ion, reforming –COOH group, leaving +ve charge Direction of Travel Speed of Movement
If alkali added, the –NH3+ part of the
zwitterion donates Voltage applied
pH of buffer solution Temperature
an H+ ion to the OH-,
reforming –NH2 group and H2O,
Charge on amino acid Size (Mr) of amino acid
leaving a -ve
charge
Magnitude of 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
Amide link formed by nucleophilic attack of –NH2 group Alkene joins to itself, no molecule lost
of
one amino acid on –COOH group of another E.g. nA →   −A − A − A − A− or (−A−) ­ n ​

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
Reaction is a condensation reaction as H2O eliminated
Longer chains with have fewer side chains have stronger
Reaction can continue to occur as product still has –NH2 VDW forces
and –COOH group present

Dipeptide → Tripeptide → Polypeptide (protein)

Proteins are polymers of amino acids; many polypeptide

chains held
together by intermolecular forces
‎ ‎
Hydrolysis: involves breaking of peptide links by reaction
polyethene polytetrafluoroethene
with
water catalysed by an acid or alkali catalyst, giving
back the amino
acids, temp. nearly 90oC
LDPE HDPE
Soft plastic made with non-
11.15. Electrophoresis polar polymer
Using Ziegler catalyst

Electrophoresis is used to separate, identify and purify Hard plastic made with non-
Highly branched chains
amino
acids obtained when protein hydrolysed polar polymer
Technique based on separating ions placed in an electric Low melting point Unbranched chains
field. When
sample placed between two electrodes: Chains cannot pack closely
+ve charge ions move towards –ve charged electrode due to random branching High melting point
–ve charge ions move towards +ve charged electrode leaving gaps
Closely packed chains, less
= low density
gaps
= high density

12.2. Natural and Synthetic Rubber

Sample placed on absorbent filter paper (or gel)
Buffer solution carries ions along (back or forth) Rubber is formed (naturally and synthetically) by addition
polymers
Factors that Determine the
 

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Natural Rubber:  
Nylon 6, 6

Monomers:

isoprene natural rubber

‎
Hexandioic acid 1, 6-diaminohexane
12.3. Condensation Polymerization
Polymer:
When two different molecules (monomers) react together
to form an
ester or amide bond with the elimination of a
small molecule
(H2O or HCl)

Polyamides Polyesters
Monomers joined by ester
Monomers joined by amide
link: ‎
(peptide) link:
 
Nylon 6

Monomer: contains both NH2 and COOH group

Caprolactam is a cyclical compound and when heated
at
260oC, cycle breaks and polymerizes
12.4. Examples of Polyesters
Synthetic polyesters: terylene
Natural polyesters: fats
Caprolactam nylon 6
   
Terylene Properties of Nylon:
  High tensile strength: due to H-bonds between chains of
Monomers: polymers;
the N and O atoms with H
Elasticity: single covalent bonds within polymer, chains
are free to
rotate
Low density: unbranched chains, no gaps

Ethane-1, 2-diol 1 Hence very useful fibre in clothing industry

 
Kevlar:

4-benzenedicarboxylic acid Monomers:

Polymer:

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

Used for spinning into fibres Polymer

12.5. Examples of Polyamides

Synthetic polyamides: Nylon and Kevlar
Natural polyamides: proteins

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Extremely strong: delocalization of π e-s beyond

benzene A nitrogen-containing base
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
Proteins: a natural polyamide; many polypeptide chains 12.8. DNA Replication
held together
by intermolecular forces
Amino acid residue: an amino acid unit within a Process of copying DNA during cell division
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.
serine Enzymes catalyse the polymerization reaction
alanine 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,
polymerization of
nucleotides. the incoming
nucleotide is selected for its ability to
pair with base in the
old strand
  H-bonding plays an important role in the recognition
Functions of deoxyribonucleic acid (DNA): as
different number of H-bonds involved in each pair
Can make copies of itself so that genetic information can
be pass on
from generation to generation 12.9. Non-solvent based Adhesives
Contains sequence of bases that form genetic code used
to synthesize
proteins Silyl modified polymers (SMP):

 
Nucleotides in DNA are made up of:

A polymer that contains silicon bonded to oxygen

A sugar called deoxyribose
They set by reacting with moisture in air; water
A phosphate group
hydrolyses
silicon-oxygen parts, forming cross-linkages

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Effectively bonds polymer chains to each other with

12.11. Degradable Polymers
strong covalent
bonds of siloxane cross-linkage

  Disadvantages of plastics:
Epoxy Resins: Non-biodegradable
On combustion, give out harmful vapours
Example of thermosets: polymers that form extensive
networks of
covalent cross-links  
Very strong and cannot be melted and remoulded Biodegradable Plastics:
Formed by reacting a monomer with expoyethane
Can contain small amounts of starch: bacteria and fungi
(triangular molecule
CH2CH2O) and a diamine are mixed
in moist
soil can break it down into smaller compounds,
For example: 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:
Polyamides broken down to carboxylic acids & amines
Polyesters broken down to carboxylic acids & alcohols
The polymer produced forms a giant network of cross-
linking with
other polymers:  
Photodegradable Plastics:

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

ultraviolet waves
Causes bonds in region of carbonyl group to weaken and
break
Disadvantages:
Superglue: Plastic usually buried under ∴ cannot get sunlight
If recycled, products are weaker
Uses addition reaction to stick objects together
The monomer is CH2­=C(CN)COOCH3, methyl
cyanoacrylate, and addition takes place across C=C 13. Entropy & Gibb’s Free
Energy
13.1. Entropy Change
Polymerisation initiated by presence of moisture
Entropy: measure of the ‘disorder’ of a system
A system becomes more stable when its energy is spread
12.10. Conducting Polymers out in a more
disordered state
Spontaneous change: a change that tends to happen
Polymers generally insulators but ethyne can conduct
naturally;
once started, the change will carry on
electricity
Spontaneous changes may not be instantaneous or
happen rapidly; most
are slow and need an input of
energy to start

13.2. Changing Entropy

Contains alternate single & double carbon-carbon bonds As a substance changes state from (s) → (l)
→ (g); its
Can conduct electricity because p-orbitals on entropy increases as molecules become more
disordered
neighbouring carbon
atoms overlap resulting in long When an ionic salt is dissolved in water (s) → (aq);
the
bands of delocalized π
e-s free to move along the chain entropy increases as as the crystal breaks up and the ions
Doping: other substances, such as iodine, added to find
their way between the water molecules
improve
electrical conductivity of polymer Increasing the temperature of a substance (without
Advantages over metal conductors: changing state)
increases entropy e.g. when heating a
Do not corrode gas, the number of different
possibilities for arranging
Much less dense the energy over the molecules increases.
Shaped more easily If a reaction increases the number of gas molecules, the
E.g. made into thin sheets to make flat panels that light entropy
increases as gases have higher entropies than

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solids or liquids δGθ = 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:
13.3. Entropy Change in Exo/Endo ‎∆G State of Reaction Stability of Compound

Reactions -ve Spontaneous More stable

+ve Not Spontaneous Less stable
Exothermic Reactions Endothermic Reactions 0 Equilibrium -
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
ΔGθreaction = ΔGθ2 − ΔGθ1
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

If ΔHreaction
θ in kJ
mol-1, change to J by × 1000
​

Negative sign part of equation, always put it Enthalpy-driven reaction: flow of thermal
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 ΔStotal
θ positive, reaction
is feasible If ‎∆H < T∆S provides most of the free energy in the
reaction
​

13.5. Entropy in Equilibrium Reactions

13.9. Temperature Change & Reaction
At position of equilibrium, the total entropy change of Spontaneity
forward
reaction equals the total entropy change of
backward reaction For exothermic reaction:
Under standard reactions, the overall entropy change is if temperature is increased
zero
T ΔS value becomes more +ve
ΔG +ve ∴ less likely to be
spontaneous
13.6. Gibbs Free Energy For endothermic reaction:
if temperature is increased
ΔG = −T ΔS total ​

T ΔS value become more -ve

Gibbs free energy (G): amount of energy in a system that
ΔG -ve ∴ more likely to be
spontaneous
is available to do useful work
Standard molar Gibbs free energy of formation
(ΔGθf ): ​

14. Analytical Techniques

the free energy change that accompanies the formation
of one mole of a compound from its elements in their
standard state 14.1. Paper Chromatography

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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 used on smaller
samples
Stationary phase: immobile phase in chromatography For colourless spots:
that 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 accumulate on spots which appear dark brown
partition from mobile phase to the stationary phase Place plate under UV light; the glow is reduced by
solutes which
appear as dark spots on the bright plate
Depending on solubility, the solutes migrate at different
rates and
travel up to different distances
Partition: separation due to different solubilities of
14.4. Gas/Liquid Chromatography
compound
in two solvents
Used to separate and identify very small samples of
The more polar a solute component is, the less it travels
gases, liquid
and volatile solids
as there
are stronger H-bonds to H2O of st. phase
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 The vaporized sample is carried by an inert gas (mobile
phase) over
the surface of a liquid (stationary phase)
in which chromatography is carried out must be identical
When stationary phase is non-polar, rate of movement is
to those
quoted in Rf data table (e.g. temp, solvent)
determined principally by volatility
Distance Moved by Solute Spot When stationary phase is polar, it will tend to retain polar
Rf = components of the mixture
Distance Moved by Solvent Front
​ ​

Components of a mixture leave the column after definite

Colourless chromatograms can be seen by spraying a intervals of
time and are monitored by a detector
locating agent
(e.g. ninhydrin) to reveal spots 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
1
carried out
again by rotating the chromatogram 90o and × base × height
2
​

re-running in
a different solvent
‎

14.3. Thin Layer Chromatography

Peak Area of X
e.g. % of X
= Sum of Areas of X and Y
As solute rises with solvent, they get separated from
​

mobile phase
and adsorbed to the stationary phase Technique Separation Method
Adsorption: separation due to different attraction Paper chromatography Partition
between the
compound and the stationary phase, Thin-layer chromatography Adsorption
relative to their solubility in
the solvent Gas/liquid chromatography Partition
The solid in stationary phase is either Al2O3
or SiO2; it is
spread onto a microscope slide as a slurry
using water
and then dried into a white coating 14.5. Mass Spectrometry

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The mass spectrometer:

A vaporized sample is injected through the vapor inlet

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

TMS is considered as 0 and all other compounds are

Identifying Cl and Br using [M+2] and [M+4] peaks
compared by
quoting shift away from TMS line
Percentage abundance of Cl and Br isotopes Low Resolution NMR:
Shows single peaks for each non-equivalent H-atoms
Isotope Approx. % Isotope Approx. % Relative peak areas proportional to no. of H-atoms
35Cl 75% 79Br 50% Can use shift value to identify type of H-atom present
High Resolution NMR:
37Cl 25% 81Br 50% The NMR signal is also affected by magnetic field of H-
atoms on
neighbouring C atoms

14.7. Proton (1H) NMR Spectroscopy Causes peaks to split in particular patterns due to
spin-spin
splitting

14.8. (n + 1) Rule
n hydrogens on an adjacent carbon atom will split a peak
into
n + 1 smaller peaks

No. of Adjacent 1H Splitting Ratio of Peak

atoms Pattern Heights

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No. of Adjacent 1H Splitting Ratio of Peak 14.11. Carbon-13 NMR Spectroscopy

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

of hydrogens
attached to the carbon atom next door
15. Organic Synthesis
14.9. Identifying –OH or –NH Signal
15.1. Chiral Drugs from Natural Sources
The –OH signal always appears as a single peak because
the H atom is
exchanged rapidly with those in water Most chiral drugs extracted from natural sources often
causing it to appear
unaffected to spin-spin splitting contain only
a single optical isomer.
In biological systems, molecules are synthesized and
ROH + H2O $\rightleftharpoons$ RO + H3O
broken down by
reactions involving enzymes
Deuterium is an isotope of hydrogen that behaves These reactions work by a lock-and-key mechanism and a
chemically like H
but different magnetic properties to H molecule has
to be the right shape to fit the enzyme
so don't produce peaks in the
area of spectrum with H Different arrangements around a chiral center will force
Organic compounds are shaken with deuterium oxide an entirely
different shape on the molecule, and it may
(D2O)
and the H-atoms bonded to electronegative atoms no longer fit the enzyme
(–OH and –NH) are
replaced; deuterium exchange So enzyme systems will tend to produce a single optical
isomer
because that is the only shape, they work with
ROH + D2O $\rightarrow$ ROD +DHO
When this is done, the NMR signal due to –OH and –NH 15.2. Synthesis of Chiral Drug Molecules
hydrogen
disappears, confirming that the peaks were caused
by those groups Each chiral center will have two possible arrangements of
bonds
around it and a different arrangement of bonds
14.10. Describing an NMR Spectra will mean a
differently shaped molecule
Differently shaped molecules won't necessarily fit the
For example: 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
is more
potent; better therapeutic activity
Minimizes risk of side effects thereby protecting
To identify the protons present, set up a table as follows patients from
further problems
Reduces cost of production because all that is
No. of Chemical Type of Splitting No. of H on produced can be
used as the drug
H shift proton pattern adj. C Producing pure enantiomers:
3 1.30 -CH3 Doublet 1 Optical resolution: the drug is produced following
traditional synthesis route and then a single
6 3.30 -O-CH3 Singlet 0
enantiomer is
separated physically by adding a
1 4.60 -O-CHR2 Quartet 3 substance that reacts with the
other isomer
Optically active starting material: drug produced from
Final molecule: (CH3O)2CH-CH3 optically active starting material (e.g. carbohydrates or

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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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Chemistry (9701)

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