1819 Physical and Inorganic Summary PDF

Jurong Pioneer Junior College
X)
2019 JC2 H2 Chemistry (9729)
PHYSICAL & INORGANIC CHEMISTRY SUMMARY
(LT
Section A: Physical Chemistry Summary
Topic
1 Atomic Structure
Content Page
KEEP CALM
14
2 Chemical Bonding 59 AND
3 The Gaseous State 10  11
4 Atoms, Molecules and Stoichiometry 12  16 EXCEL IN
5 Chemical Energetics 17  22
6 Reaction Kinetics 23  28
7 Chemical Equilibrium 29  31 CHEMISTRY
8 Galvanic Cells
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9 Electrolytic Cells 36  38
16 Acids, Bases & Solubility Equilibria 39  44
Section B: Inorganic Chemistry Summary

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Topic Content Page
11 The Periodic Table (Period 3 Elements) 45  49
11 The Periodic Table (Group 2 Elements) 50  51
11 The Periodic Table (Group 17 Elements) 52  53
21 Introduction to Transition Elements 54  59
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Co
* Physical & Inorganic Chemistry Summary is prepared and compiled by Ms Lee Tian Xin.
Adapted and modified from JJC past year Physical and Inorganic Chemistry Summary.
Topic 2 : Atomic Structure
X)
1 Subatomic Particles...
sub–atomic particle location in atom rel.charge rel. mass
mass/nucleon no. = p + n
neutron (n) nucleus 0 1
proton/atomic no. = p
proton (p) nucleus +1 1
around nucleus 1
electron (e) –1
(in fixed energy levels) 1840
 Atom is electrically neutral (i.e. no. of p = no. of e ). –
(LT
Ion is electrically charged (i.e. no. of p ≠ no. of e–)  cation: no. of p > no. of e–
 anion : no. of p < no. of e–
 Isotopes are atoms of the same element with same number of protons but different number of neutrons
(i.e. same atomic no. but different mass no.).
 similar chemical properties  same number and arrangement of e–
 different physical properties  different no. of neutron (i.e. different mass no.)
 Isoelectronic: same number of e but may or may not have same electronic configuration.
Isotonic: same number of neutrons.
2 Behaviour of Particles under the effect of Electric field...
 Direction: opposite attracts

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The deflection pathway is dependent on: deflection occurs
straight line path
charge after leaving field
 Angle:  of deflection  –
mass p
n
p, n, e
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deflection starts only +
upon entering field e
3 Electronic Configuration...
nucleus ATOM principal quantum shells (pqs)

is made up of
contains contains
protons and neutrons subshells orbitals contains

electrons
consists
(s, p, d & f) (px, py, pz etc)
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 Within each subshell of the same pqs, the orbitals are degenerate (i.e. orbitals of same subshell have
same energy). Example: The electrons in 2px, 2py and 2pz have same energy).
 The size and energy of orbitals of same subshell increases with principal quantum number (i.e. 2s
orbital is larger and has higher energy than 1s orbital but both have the same spherical shape) as the
electrons are further away from the nucleus and hence, weaker the nuclear attraction.
 Notation for electronic configuration:
s,p,d,f notation
Co
Electronsinbox notation
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 1 Topic 1: Atomic Structure

(Adapted from past year JJC Physical Summary)
 Shapes of orbitals (must know how to draw!)
X)
s orbital (spherical) p orbital (dumb–bell shaped)
(LT
 Rules for writing electronic configuration
 Aufbau Principle: Electrons fill orbitals of lowest energy first before moving to
an orbital of next lowest energy and so on.
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(Note: Fill 4s then 3d orbitals!)
 Hund’s Rule : When electrons are added successively to a set of degenerate

orbitals, they must occupy these orbitals singly first and with
parallel spins before pairing begins so as to minimise inter–
electronic repulsion.
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 Configuration of Ions: Always write the electronic configuration of atom first!

(Cations) Remove e from the outermost shell (Note: Remove from 4s then 3d!)
(Anions) Add e to outermost shell
 Position in Periodic Table: Use this to derive electronic configuration quickly.

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Co
Exceptions: Cr is [Ar] 3d5 4s1, not 3d4 4s2!

Cu is [Ar] 3d10 4s1, not 3d9 4s2!
The extra stability of d5 and d10 configuration is due to the symmetrical 3d electrons cloud
which minimizes electronic repulsion. This transition of electrons is only possible as the 3d and
4s electrons have similar energies.
4 3– Radius (atomic or ionic) depends on:
 P S2–  nuclear charge
 Cl–
X)
Na  no. of quantum shell with electrons
Mg 
Al  shielding effect by inner shell electrons
Si
radius /nm
P
S Strategy:
Cl
 Ar 1) Write electronic configuration
Na+ 2) Apply the above 3 factors.
Mg2+ 3) Conclude on nuclear attraction.
Al3+
Si4+
* If the 3 factors are the same, the reason to use
(LT
is due to mutual repulsion between electrons.
atomic number
Across the period, the nuclear charge increases while the number of quantum shell with electrons is the
same and the shielding effect by inner shell electrons is relatively constant.
The nuclear attraction on the outermost electrons increases and the radius decreases.
Down the group, the nuclear charge increases while the number of quantum shell with electrons increases
and the shielding effect by inner shell electrons increases.
The nuclear attraction on the outermost electrons decreases and the radius increases.
With reference to the diagram above,

 Cation has smaller radius than its corresponding atom (e.g. Mg2+ vs Mg) since the cation has one less
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quantum shell of electrons and less shielding effect after the removal of outermost electrons.
 Anion has a larger radius than its corresponding atom (e.g. S vs S2–) due to greater electron–electron
repulsion when electrons are added to the same outermost shell, resulting in the expansion of electron
cloud.
 Across each isoelectronic series with same electronic configuration (e.g. from Na+ to Si4+ or from P3– to
Cl–), the nuclear charge increases while the number of quantum shell with electrons is the same and the
shielding effect by inner shell electrons is relatively constant.
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The nuclear attraction on the outermost electrons increases and the radius decreases.
5 Ionisation energies…
First IE is the energy required to remove one mole of electrons from one mole of GASEOUS ATOMs of
the element.
1st IE : M(g)  M+(g) + e– H > 0
2 IE : M (g)  M (g) + e
nd + 2+ – M(g)  M3+(g) + 3e (Sum of 1st , 2nd and 3rd IEs of M)
3rd IE : M2+(g)  M3+(g) + e–
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 nth IE of consecutive elements

IEs depends on:
IE /kJ mol–1  nuclear charge
ns2  distance of the outermost e from nucleus
np6  shielding effect by inner shell electrons
 ns2  Strategy:
np3
ns2 1) Write electronic configuration
np5 2) Check if it is one of the 2 anomalies.

Co
ns2 ns2
If not, apply the above 3 factors.
ns2 np4
ns1 3) Conclude on nuclear attraction.
np2
ns2
np1
 (n+1)s1
Atomic no.
 Across the period, the nuclear charge increases and the distance of outermost electrons from the
nucleus decreases while the shielding effect by inner shell electrons is relatively constant.
X)
The nuclear attraction on the electron to be removed increases and the 1st IE generally increase.
 Down the group, the nuclear charge increases while the istance of outermost electrons from the
nucleus increases and the shielding effect by inner shell electrons increases.
The nuclear attraction on the outermost electrons decreases and the IE decreases.
With reference to the above IE graph,

 Mg: 1s2 2s2 2p6 3s2 Al: 1s2 2s2 2p6 3s2 3p1
(LT
1st IE of Al is lower than that of Mg because the 3p electron of Al is further away from the nucleus
and has a higher energy than the 3s electron of Mg.
Al+: 1s2 2s2 2p6 3s2 (Mg) Si+: 1s2 2s2 2p6 3s2 3p1 (Al)
2 IE of is Si lower than that of Al because 3p electron of Si+ is further away from the nucleus and
nd
has a higher energy than the 3s electron of Al+.
 P: 1s2 2s2 2p6 3s2 3p3 S: 1s2 2s2 2p6 3s2 3p4
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1 IE of S is lower than that of P because of the interelectronic repulsion between the paired 3p
electrons in S makes it easier to remove one of the paired electrons than the unpaired 3p electrons
of P which do not experience such repulsion.
S+: 1s2 2s2 2p6 3s2 3p3 (P) Cl+: 1s2 2s2 2p6 3s2 3p4 (S)
2nd IE of Cl is lower than that of S because of the inter–electronic repulsion between the paired 3p
electrons in Cl+ makes it easier to remove one of the paired electrons than the unpaired 3p
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electrons of S+ which do not experience such repulsion.
 Successive IEs of an element

IE / kJ mol1 Feature  (Successive IEs increases)
 1st IE < 2nd IE < 3rd IE <… because with
each successive removal of electron,
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increasing amount of energy is
required to remove a negatively
 charged electron from an increasingly
positively charged ion as there is
greater electrostatic attraction between
the electrons and nucleus.

Feature : (1st sharp increase in IE)
The sharp increase from 2nd to 3rd IE
implies that the 3rd electron is removed
from the next inner quantum shell.
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Hence, the element has 2 valence

electrons and it is a Group 2 element.
no. of e removed
Feature : (Moderate increase in IE)
The moderate increase from 8th to 9th IE implies that the 9th electron is removed from another subshell,
ns, which is closer to the nucleus and has lower energy.
Feature : (No. of sharp increase in IE)

The number of sharp increase indicates the total number of inner quantum shell the element has. Hence,
Co
the total number of quantum shell (i.e. Period number) is the number of sharp increase + 1.

Topic 2: Chemical Bonding
X)
1 Chemical Bonds...
Chemical bonds is electrostatic force of attraction between a +ve entity and a ve entity.
 Ionic : between cation and anion
 transfer of e due to large EN difference
Covalent : between +ve nuclei of the two atoms & the bonding e between them
 sharing of e due to small EN difference
: between metal cation and its mobile valence e
(LT
Metallic
IMF : between + end of a molecule and  of another molecule
Recognise that bonding is a continuum in terms of EN difference

nonpolar polar ionic bond with purely
covalent bond covalent bond some cov. char ionic bond
EN difference
negligible small relatively large large
difference difference difference difference
Electron cloud shared Electron cloud shared Depend on extent of polarisation
equally between two unequally between of anion by cation:
atoms of the same two atoms of different  Polarising power of cation
elements or C–H or elements. ( charge density)
P–H bond The more EN atom  Polarisability of anion MUST know examples:
bears the  charge. ( size of anion)  AlCl3, AlBr3, AlI3, BeCl2, BeBr2,
Larger the extent of BeI2 are essentially covalent.
X X polarisation, greater the  AlF3,Al2O3, BeF2, BeO are
H X covalent char. in the ionic bond essentially ionic.
ht Chemical Bonding
Ionic Bonding Covalent Bonding Metallic Bonding

(includes dative covalent bonding)
Giant Ionic Giant Metallic
Structure Structure
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Simple Molecular/Covalent Giant Molecular/Covalent
Structure structure
discrete molecules
held by : Limited eg: graphite,
diamond, silicon, SiO2
INTERMOLECULAR FORCES
Between Between
Nonpolar molecules Polar molecule
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(with no net dpm) (with net dpm)
instantaneous dipole
–induced dipole permanent dipole Hydrogen Bond
attractions –permanent dipole (molecules with
attractions –NH, –OH or –FH bond)
2 Dative Bonds...
Dative bond is is a single bond in which the two bonding electrons are both contributed from only one
Co
atom. (i.e. A: B, where A is the electron donor and B is the electron acceptor)
Criteria to form dative bond: Molecules with Be/Group 13 central atom are electrondeficient
and tends to accept lone pairs from another molecule/ion via
a) one atom of a species has at least 1 lone pair dative bond formation, to achieve a stable octet configuration
(e donor, Lewis base)
b) one atom of another species have at least
1 empty orbital (e acceptor, Lewis acid)
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 5 Topic 2: Chemical Bonding

3 Dot–and–cross Diagrams, VSEPR, Bond Angles, Shapes, Hybridsation, Polarity...
 Valence shell electron pair repulsion (VSEPR) theory states that
X)
(a) electron pairs (i.e. bond pairs and lone pairs) around the central atom arrange themselves as far
as possible in space to minimise mutual repulsion;
(b) lone pair–lone pair repulsion > lone pair–bond pair repulsion > bond pair–bond pair repulsion.
 Drawing ‘dot–and–cross’ diagram and Determining Bond angles & shapes & Hybridisation...
Strategy:
a) Determine the no. of valence electrons (i.e. Group no.) each element has
(LT
b) Determine central atom (usually the less EN atom or the one with least atom)
c) For ions: Cation – remove electrons from central/less EN atom
Anion – add electron to more EN atom (use ‘’ or ‘’ or stated in Qn)
d) Complete octet structure as per normal
e) Check total no. of electrons around each atom (Can central atom expand octet?)
 If ‘yes’, the ‘dot–and–cross’ diagram is complete.
 If ‘no’, change one  bond to dative bond
f) Determine the total no. of bond pair and lone pair around central atom and apply VSEPR theory
to determine bond angle and shape.
(Note: Multiple bonds between two atoms is considered as ‘one group of bond pair’
2 electron pairs 3 electron pairs 4 electron pairs

(sp hybridised) (sp2 hybridised) (sp3 hybridised)
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5 electron pairs
For trigonal bipyramidal,

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the lone pair should be
placed on equitorial
position first to minimise
repulsion!
6 electron pairs
For octahedral, the lone

pair should be placed
on axial position first to
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minimise repulsion!
No. of electron pairs No. of hybrid Hybridisation state Arrangement of Possible bond
around central atom orbitals required of central atom hybrid orbitals angles
2 2 sp 180 
linear
3 bp, 0 lp 120 
Co
3 3 sp2
2 bp, 1 lp < 120 
trigonal planar
4 bp, 0 lp 109.5 
4 3 bp, 1 lp 4 sp 3
107 
2 bp, 2 lp tetrahedral 104.5 

Flowchart to determine if a molecule is polar or non–polar...
After determining the shape of the molecules,
X)
Note: polar bonds  polar molecule
Also has HB if there is

Has only id–id N–H, O–H or F–H bond
attraction between
molecules Has id–id & pdpd attraction
between molecules
(LT
& linear
3 Types of Covalent Bonds...

  bond is formed by head–on overlap of orbitals (can be atomic and/or hybrid orbital)
s s s p p p
Note: In all covalent bonds,  bond is always formed first. one  bond
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  bond is formed by side–way overlap of p–orbitals.
Note:  bond is only observed in multiple bonds (i.e. double/triple bond).
In all multiple bonds, one of the bonds is a  bond and the rest are  bonds.
This explains why  bond is weaker than  bond and  bond cannot be rotated.
4 Hydrogen Bonds...
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Hydrogen bond is a stronger form of pd–pd attraction.
Criteria to form Intermolecular Hydrogen bonds: Checklist for drawing diagram of hydrogen bond:
a) H atom directly bonded to highly  + on H and  on N/O/F of HN/O/F bond
electrongative N/O/F  lone pair on N/O/F of another molecule/ion
(Remember: Hopefully No One Fails!)  dotted line to show hydrogen bond
b) at least 1 lone pair on N/O/F in another  label
molecule/ion.
Hydrogen bonds can be used to explain the

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following phenomena:
 Why ice floats above water?
 Why oil floats above water?
 Why the Mr of CH3COOH in pure liquid state is
120 but 60 in aqueous state?
 Why 2–nitrophenol has a lower boiling point
than 4–nitrophenol?
Note:
For molecules which can form hydrogen bonds
Co
but is not very soluble in water, it is due to

steric hindrance (e.g. phenol).
Bulky, non–polar phenyl group hinders the

formation of effective hydrogen bonds between
phenol molecules and water molecules.
Hence, phenol is not very soluble in water.

4 Overview of Structure, Bonding and Physical Properties...
Structure Type of bond(s) present Strength of bond Physical Properties
Metallic bond depends on:  high mp (except Hg)
T
Giant strong metallic bonds: c) charge density of Mx+   conduct electricity in (s) & (l)/molten state
Metallic strong electrostatic attraction between metal charge of ion  insoluble in H2O but react with H2O
Structure cations and mobile valence electrons radius of ion  malleable & ductile (can slide without breaking the metallic
 no. of mobile valence e bond)
L
Ionic bond depends on:  high mp
strong ionic bonds: qq  conduct electricity in (aq) & (l)/molten state
Giant Ionic  |lattice energy|     soluble in H2O if the ions can form ion–dipole interaction
strong electrostatic attraction between
(
Structure r  r
with H2O molecules (Hsoln = LE + Hhyd)
cations and anions (effect of (q+q) on LE is greater than that of  brittle (ions of same charge repel and causes the ionic bond
(r+ + r) on LE to break)
strong covalent bonds: Covalent bond depends on: bond energy  high mp
Giant
strong electrostatic attraction between nuclei
t
 bond length / atomic radius  does not conduct electricity (except graphite, along the
Covalent
of 2 atoms and shared bonding electrons  bond order (CC vs C=C vs CC) layer)
Structure
 type of hybrid orbital (sp vs sp2 vs sp3)  insoluble in H2O
Within each molecule: strong covalent bond Covalent bond depends on: bond energy
strong electrostatic attraction between nuclei  bond length /atomic radius
h
of 2 atoms and shared bonding electrons  bond order (CC vs C=C vs CC)
 type of hybrid orbital (sp vs sp2 vs sp3)
id–id depends on:  low mp/bp
Between molecules: weak intermolecular force  no. of e per molecule  does not conduct electricity unless ionises in H2O
Simple  shape of molecule (same MF, isomers) (with
g
weak electrostatic attraction* between  soluble in H2O if can
Covalent branching, more spherical, smaller surface
molecules  form hydrogen bonds with H2O molecules or
Structure *id–id, pd–pd, HB (NOF) area of contact between molecules)
 ionises in H2O to give ions to form ion–dipole interactions
Simple
Monoatomic
strength of id–id < pd–pd < HB
if no. of e per molecules are similar
Between atoms:
weak id–id attractions between atoms
i
(Note: id–id is present in all molecules but it is
r
the only IMF for non–polar molecules)
pd–pd depends on:
 polarity of polar bonds
HB depends on:
 polarity of H–X bonds
 extensiveness of hydrogen bonds
id–id depends on:
 no. of e per atom
with water
 low mp/bp
 does not conduct electricity in any state
Structure
2019 JPJC J2 H2 Chemistry (9729) / LeeTX

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 insoluble in H2O
Topic 2: Chemical Bonding

5 Explaining BP/MP, Electrical Conductivity and Solubility...
X)
 Explaining melting point and boiling point...
Marking Points/Strategy: Examples:
a) Type of structure (GIS/GMS/GCS/SCS?) AlF3 has giant ionic structure while PF3 has a simple
covalent structure.
b) Amount of energy required to break More energy is required to overcome the stronger
c) type of bonds/IMF (IB/MB/CB/id–id/pd–pd /HB?) ionic bonds between Al3+ and F ions in AlF3 than
the weaker permanent dipole–permanent dipole
If they are of the same type, compare the attraction between PF3 molecules.
difference in strength using the relevant factors Hence, AlF3 has higher boiling point than PF3.
affecting the bonds/IMF (see overview in Point 4)
(LT
d) conclude Both CH3CH2Cl and CH3CH2Br have simple covalent
structure.
More energy is required to overcome the stronger
instantaneous dipole–induced dipole attraction
between CH3CH2Br molecules than those between
CH3CH2Cl molecules since CH3CH2Br has more
electrons per molecule than CH3CH2Cl.
Hence, CH3CH2Br has higher boiling point.
 Explaining electrical conductivity...

Electrical conductivity depends on: Examples:
 Presence of mobile charged carrier (mobile ions AlF3 has giant ionic structure while PF3 has a simple
and/or mobile valence electron) covalent structure.
AlF3 can conduct electricity in aqueous and liquid
 Number of mobile charged carrier
state due to the presence of mobile ions but PF3
cannot conduct electricity in all state due to the
Marking Points/Strategy:
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a) Type of structure (GIS/GMS/GCS/SCS?)
absence of mobile charged carrier.
Both Mg and Na have giant metallic structure.

b) Presence of mobile charged carrier in which
Both can conduct electricity in solid state due to
physical state?
the presence of mobile valence electrons. However,
c) If both can conduct electricity, compare the no. of Mg has higher electrical conductivity as it has more
mobile charged carrier mobile valence electrons.
d) conclude
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 Explaining solubility...
Solubility depends on: Examples:
 formation of favourable solute–solvent interactions AlF3 has giant ionic structure while PF3 has a simple
between solute particles and solvent molecules covalent structure.
Ions of AlF3 can form ion–dipole interactions with
H2O molecules but PF3 molecules cannot form ion–
Marking Points/Strategy: (for brief explanation)
dipole interactions and hydrogen bonds with H2O
a) Type of structure (GIS/GMS/GCS/SCS?) molecules.
b) Can form hydrogen bonds/ion–dipole interactions Hence, AlF3 is soluble in water but PF3 is not.
with H2O molecule
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Both MgF2 and NaF have giant ionic structure.

c) If both are soluble in water, compare Ions of both MgF2 and NaF can form ion–dipole
extensiveness of hydrogen bond or strength of interactions with H2O molecules. However, Mg2+
ion–dipole interaction) forms stronger ion–dipole interaction since Mg2+
d) conclude has higher charge density than Mg2+.
Marking Points/Strategy: (for detailed explanation ) Example:

a) energy released on forming solute–solvent Energy released upon forming ion–dipole
interaction interaction between ions and H2O molecules is
more than sufficient to compensate the energy
Co
b) sufficient to compensate?
c) energy required to break solute–solute required to break the strong ionic bonds
interaction and solvent–solvent interaction between ions.
Hence, MgF2 is soluble in water.
If the solvent is non–polar molecule (e.g. benzene), the solute must be non–polar too in order to form
favourable interaction (i.e. id–id) with the solvent molecule.

Topic 3 : The Gaseous State
X)
1 Assumptions of Kinetic Theory of Gases...
a) The gas particles exerts no intermolecular forces of attraction on one another or on the wall of
container.
b) The gas particles have negligible volume compared to the volume of gas itself.
c) The collisions between gas particles is perfectly elastic.
d) The average kinetic energy of particles in a gas is proportional to the absolute temperature in kelvin.
e) The gas particles are in constant and random motion.
(LT
Note: If you are asked to quote the assumptions, quote in the above order of importance!
2 Definition of Ideal Gas....

Ideal gas is a gas that obeys all the assumptions of kinetic theory of gases.
or
Ideal gas is a gas that obeys the ideal gas equation, pV = nRT.
p : pressure in Pa or Nm–2
V : volume in m3
pV = nRT n : amount of gaseous molecules in mol
R : universal gas constant, 8.31 J K–1 mol–1
T : temperature in Kelvin, K
Note: 1 bar = 105 Pa, 1 atm = 101325 Pa

1 dm3 = 103 m3 , 1 cm3 = 106 m3
ht
T (in K) = T (in C) + 273
Extension of formula:
Molar Mass, Mr Density,  (in g m3) Concentration, c (in mol m3)
m m m n
Since  =
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Since n = , pV = RT , Since c = ,
Mr Mr V V
p  Mr p
Mr =
mRT density,  (in g m3) = c (in mol m3) =
pV RT RT
Other formula related to gas:

 Partial pressure of a gas in a mixture is the pressure that each gas would exert if it alone occupied the
n RT n RT
container (i.e. pA = A or ptotal = total ).
V V
py
nA pA nA nA
Hence, = (i.e. p A   ptotal where is the mole fraction of gas A in the mixture.
ntotal p total ntotal ntotal
 Dalton’s Law of Partial Pressure states that the total pressure of a mixture of gases, which do not react
with one another, equals the sum of the partial pressure of component gases.
pT = pA + pB + pC + … + pn
Co
where pA, pB and etc are partial pressure of gas A, B and etc respectively.
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 10 Topic 3: The Gaseous State

3 Sketching of Graph...
Strategy:
X)
a) Rearrange pV = nRT by grouping the factors for y–axis (settle this first!) on the LHS of equation and for
x–axis on the RHS of equation.
b) Determine the relevant graph type (e.g. y = mx + c or y = c etc).
c) Sketch accordingly!
Example: p
Sketch p against V for a fixed mass of an ideal gas under constant T (i.e.
n, R and T are constant).
(LT
Let y = p and x = V,
nRT k
pV = nRT  p = (i.e. plot a graph of y = )
V x
V
4 Deviation from Ideal Gas Behaviour...

A real gas deviates most from ideal behaviour when the following two assumptions of kinetic theory of gases are
violated:
or
A real gas tends towards ideal behaviour most when the following two assumptions of kinetic theory of gases are
fulfilled:
a) The gas particles exerts no intermolecular forces of attraction on one another or on the wall of
container.
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b) The gas particles have negligible volume compared to the volume of gas itself.
real gas
n ideal gas
deviation from ideal
gas behaviour
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p
 Effect of Pressure (under constant T):
At high pressure, the volume of gas is small and hence, the volume of gas particles is significant
compared to that of gas. Hence, a gas deviates more from ideal gas behaviour at high pressure.
Also, when the volume of gas is small, the gas particles are closer to each other and hence, the intermolecular
force of attraction between the gas particles becomes significant.
 Effect of Temperature (under constant p):

At low temperature, the gas particles have less kinetic energy and do not have sufficient energy to
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overcome the intermolecular force of attraction between the gas particles. Hence, a gas deviates more
from ideal gas behaviour at low temperature.
Also, when there is intermolecular force of attraction, the volume of gas is smaller and hence, the volume of gas
particles is significant compared to that of gas.
 Nature of gas (for comparison between two different gases):

 When a gas has more electron per molecule, the strength of id–id between the molecules is stronger
and hence, the intermolecular force of attraction becomes more significant.
Also, with more electron per molecule, the volume of gas particle is larger due to larger radius and hence,
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the volume of gas particles is significant compared to that of gas.

Hence, the gas with more electrons per molecules deviates more from ideal gas behaviour.
 A polar molecule has stronger pd–pd attraction (or hydrogen bonds) between molecules than the
weaker id–id attraction between non–polar molecule.
Hence, a polar gas molecule deviates more from ideal gas behaviour.
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 11 Topic 3: The Gaseous State

Topic 4: Atoms, Molecules and Stoichiometry
X)
1 Definitions...
 Relative isotopic mass: ratio of the mass of 1 mole of atoms of an isotope to 1 of the mass of
12
1 mole of 12C atoms. (No units)
 Relative atomic mass, Ar: ratio of the average mass of 1 mole of atoms of the element to 1 of
12
12
(LT
the mass of 1 mole of C atoms. (No units)
Formula: Ar   relative isotopic mass  relative abundance 
 Relative molecular mass, Mr: ratio of the average mass of 1 mole of molecules to 1 of the mass of
12
1 mole of 12C atoms. (No units)
Formula: Mr    Ar of all atoms present in one molecule 
 Relative formula mass, Mr: ratio of the average mass of 1 mole of a formula unit of an ion or
ionic compound to 1 of the mass of 1mole of 12
C atoms. (No units.)
12
Mr    Ar of all atoms present in one formula unit of ionic compound 
ht
 A mole of any substance: the amount of substance that contains the same number of particles as
there are atoms in 12.0 g of 12C isotopes (i.e. 1 mole of particles contains
6.021023 particles).
The term “particles” refers to atoms, molecules, ions or electrons etc.
 Avogadro constant, L: the number of carbon atoms present in 12.0 g of 12C (i.e. 1 mole of 12
C
atoms has 6.021023 carbon atoms) Units of L: mol–1.
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 Empirical formula: the formula that shows the simplest whole–number ratio of the number
of atoms of each element present in the substance.
(e.g. empirical formula of butane is C2H5, glucose is CH2O
 Molecular formula: the formula that shows the actual number of atoms of each element in
one molecule of the compound. It is a simple multiple of the empirical
formula.
(e.g. molecular formula of butane is C4H10, glucose is C6H12O6.)
2 Important Formulas...
concentration
py
(mol dm–3)
× vol. of solution  vol. of solution

(dm3) (dm3)
vol. of gas × 24.0 or 22.7 (dm3 mol–1) amount × (6.02 × 1023) no. of particles
(dm3)  24.0 or 22.7 (dm mol )
3 –1 (mol)  (6.02 × 10 )23 (no units)
 molar mass
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× molar mass
(g mol–1) (g mol–1)
mass of substance
(g)
Note: Molar mass of a substance is numerically equal to its Mr. However, Mr has no units while the units of
molar mass is g mol1.
[[
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 12 Topic 4: Atoms, Molecules & Stoichiometry
3 Calculation using Composition by Mass...
Ar of element  mole ratio
 100 %
X)
mass of an element present in a compound =
Mr
Strategy: Example:
a) Use ‘MAR’ table to determine empirical formula! C H
b) (For simple covalent structure only) mass in 100 g / g 82.8 17.2
amount / mol 6.90 17.2
Use Mr of compound to determine molecular formula! ratio 1 2.50
2 5
5 3 1 2
(LT
Note: 1.25 = ; 1.50 = ; 0.333 = ; 0.667 = Empirical formula is C2H5.
4 2 3 3 Molecular formula is C2nH5n.
4 5
1.33 = ; 1.67 =
3 3
4 Calculation using Combustion data (volume of gases)...

V2 n2
Using ideal gas equation, pV = nRT, V  n under same T & p (i.e. =  volume ratio = mole ratio).
V1 n1
General Equation (for complete combustion in excess O2):
y y
at r.t.p CxHy(g) + (x + )O2(g)  xCO2(g) + H2O(l)
4 2
y
mole ratio 1 (x + ) x –
volume ratio 10 cm3

ht 4
10(x +
y
4
)cm3 10x cm3 –
Compared to gases, volume of liquids are negligible.
Before After reaction & After reaction

reaction cooled to r.t.p with NaOH(aq)
Strategy
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VCxHy combustion alkali
VCO2 a) Find VCO2 to
+ VO2, reacted first  in volume of second  in
VO2, unreacted
+ VO2, unreacted determine x.
+ VO2, unreacted gases volume of gases b) Find VO2, reacted to
VCxHy determine y.
+ VO2, reacted VCO2
 VCO2
5 General strategy to solve stoichiometry questions...
EARS: Write Equation  Calculate Amount  Apply mole Ratio  Solve the question!
py
Note: If the amount of more than 1 reagent used is known, you need to determine the limiting reagent and
use its amount to do subsequent mole ratio and calculation!
Other useful formula:

actual mass of product formed
 % yield =  100 %
theoretical / max mass of product
Theoretical/Max mass is calculated based on the limiting reagent, assuming 100 % conversion and no
product lost during the reaction.
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mass of pure compound

 % purity =  100 %
mass of impure compound
6 Scaling up/down versus Dilution...
 Scale up/down: Take V cm3 of solution from a stock solution of Vtotal cm3.
X)
(i.e. concentration of both solution is the same but amount is different)
[X] in VA cm3 of solution = [X] in VB cm3 of solution Example

n(A) in 25.0 cm3 of FA1 = x mol
VA VB
n(X in VA cm3)  = n(X in VB cm3)  250
1000 1000 n(A) in 250 cm3 of FA1 = x 
25.0
VA
 n(X in VA cm3) = n(X in VB cm3) 
VB
(LT
 Dilution: Take V cm3 of a stock solution and dilute it to Vtotal cm3 using deionised water.
(i.e. amount in both is the same but concentration is different)
n(X) in V1 cm of FA1 (original) = n(X) in V2 cm3 of FA2 (diluted)
3
V1 V2
c1  = c2   c1V1 = c2V2
1000 1000
7 Back–Titrations Calculations...
Back–titration is useful for determination of insoluble substances and difficult to titrate directly. The process
usually occurs via two separate reactions.
Reaction 1: A known excess of one reagent A is allowed to react with an unknown amount of B (which is
usually the limiting reagent).
ht
Reaction 2: The amount of unreacted A is then determined by titration with a standard solution C of
known concentration.
The amount of reacted A is calculated by subtraction and the amount of B present can then be found by
simple stoichiometric ratio of A and B.
total n(A) added = n(A) reacted with B + n(A) reacted with C
rxn 1 rxn 2
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Strategy: Apply EARS twice!
a) Write balanced Equations for both reactions
b) Calculate Amount of reagent C used
c) Use mole Ratio for reaction 2 to calculate n(unreacted A).
d) Solve for Amount of A that reacted with B by subtraction.
e) Use mole Ratio for reaction 1 to calculate amount of B.
f) Solve the question.
8 Double Indicator Titrations...

Carbonate ions (CO32) reacts with excess acid in 2 steps:
Reaction 1 : CO32–(aq) + H+(aq)  HCO3–(aq) (end–point determined by phenolphthalein)
py
Reaction 2 : HCO3–(aq) + H+(aq)  CO2(g) + H2O(l) (end–point determined by methyl orange)

Overall : CO32–(aq) + 2 H+(aq)  CO2(g) + H2O(l)
pH
Case 1: Only CO32– present in original sample
Since 1CO32(original)  1HCO3(produced),

810 × reaction 1 completed
Co
volume of HA for reaction 1 = x cm3

volume of HA for complete reaction = 2x cm3 35 × reaction 2 completed
volume of
0 monobasic
x 2x
acid used
/cm3
Case 3: CO32– & HCO3 present in original sample pH
For CO32 in the original sample:
X)
Since 1CO32(original)  1HCO3(produced),
volume of HA for reaction 1 = x cm3 810 × reaction 1 completed
volume of HA for complete reaction of CO32
= 2x cm3
35 × reaction 2 completed
For HCO3 in the original sample: volume of
0 monobasic
x 2x + y
(LT
volume of HA for reaction 1 = 0 cm3 acid used
volume of HA for reaction 2 = y cm3 /cm3
volume of HA for complete reaction of HCO3
= y cm3
total volume of HA required = (2x + y) cm3
9 Redox Reaction...
Redox reactions involve transfer of electrons between the two reactants involved.
Oxidation involves a: Reduction involves a:
(a) gain of oxygen loss of oxygen
(b) loss of hydrogen gain of hydrogen
(c) loss of electrons gain of electrons
 results in an increase in ON  results in a decrease in ON
ht
 Oxidising agent (oxidant) oxidises others while itself is reduced in a redox reaction.
Reducing agent (reductant) reduces others while itself is oxidised in a redox reaction.
 Disproportionation is a redox reaction in which one species is simultaneously oxidised and reduced.
Example: Cl2 + 2OH  Cl + ClO + H2O
(ON of Cl decreases from 0 in Cl2 to 1 in Cl and also increases from 0 in Cl2 to +1 in ClO)
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 Some rules for oxidation states...

For an atom in its elemental form, ON = 0 E.g. ON of Na = 0 ; ON of O in O2 = 0
For a monoatomic ion, ON = charge of the ion E.g. ON of Mg in Mg2+ = +2 ; ON of Br in Br = 1
For a polyatomic ion, sum of ON = charge of ion E.g. MnO4 : x + 4y = 1 ; Fe2O3 : 2x + 3y = 0
 Some common oxidation states...

Some atoms nearly always have the same oxidation number in their compounds.
All Group 1 metals +1 (valency of 1)
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All Group 2 metals +2 (valency of 2)

Al +3 (valency of 3)
Hydrogen, H +1
1 (in metal hydrides, eg. LiAlH4, NaBH4)
Oxygen, O 2
1 (in peroxides, eg. H2O2, Na2O2 and BaO2)
+1 (with fluorine, eg. F2O)
Fluorine, F 1 (most electronegative atom)
Halogen, X (other than F) 1
Co
+x (with electronegative atom like F and/or O)
9 Balancing Half–equation and Redox equation...
 All balanced equations must satisfy two criteria:
X)
 Conservation of Mass (i.e. atoms on both sides balanced)
 Conservation of Charge (i.e. overall charge on both sides balanced)
 Half–equation must have electrons on either side of equation depending it is [R] or [O].
Overall redox equation does not have electrons as total ne lost = total ne gained.
 Rules for balancing half–equations (KOHe method)

a) Identify Key element oxidised/reduced (using change in ON) and balance the atoms of key element.
b) Balance Oxygen using H2O.
(LT
c) Balance Hydrogen using H+.
d) Balance overall charge using electrons.
 Obtaining Overall redox equation from two half–equations

e) Multiply each half–equation by appropriate factors to equate the number of electrons.
total ne gained = total ne lost
f) Combine the two half–equations and eliminate any common species (e.g. e–, H2O, H+, OH–).
g) If the redox reaction in under alkaline medium,
Add appropriate no. of OH– to BOTH sides of equations (i.e. to convert H+ to H2O) then simplify the
equation.
10 Calculating unknown oxidation number...

Golden rule of redox: total ne gained = total ne lost
EARS: Write Equation  Calculate Amount  Apply mole Ratio  Solve the question!
Strategy:
ht Example:
a) Using the given/known product/reactant during The compound NH2OH is oxidised by Mn3+, which itself
redox, write relevant half–Equation. is reduced to Mn2+. 25.0 cm3 of 0.100 mol dm –3 NH2OH
required 25.0 cm3 of 0.200 mol dm–3 Mn3+ for complete
b) Calculate Amount of reagents given. reaction. What change in oxidation number does the
c) Determine the mole Ratio between species nitrogen in NH2OH undergo?
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reacted and electrons transferred E: [R]: Mn3+ + e–  Mn2+ (i.e. Mn3+  e–)
d) Solve question 25.0
A: n(Mn3+) reacted = 0.200  = 0.00500 mol
1000
25.0
n(NH2OH) reacted = 0.100  = 0.00250 mol
1000
R: From the amounts calculated, 2Mn3+  1NH2 OH.
Since 1Mn3+  1e, 2Mn3+  2e  1NH2OH.
 1 NH2OH lost 2 electrons.
or
ratio Mn3+ : e : NH2OH
py
0.00500 0.00500
0.00500 0.00250
2 : 1
 1 NH2 OH lost 2 electrons.
S: Final ON of N = (–1) – 2(–1) = +1

ON of N changes from -1 to +1.
Co
Topic 5 : Chemical Energetics
X)
1 Endothermic versus Exothermic...
 Exothermic (H < 0): heat is released/lost from the system to the surroundings (e.g water)
 products have lower energy content than reactants
 temperature of the surroundings increases
 Endothermic (H > 0): heat is absorbed/gained into the system from the surroundings
 products have higher energy content than reactants
(LT
 temperature of the surroundings decreases
Exothermic reaction Endothermic reaction

–1
energy /kJ mol energy /kJ mol–1
reactant product
ΔH < 0
ΔH > 0
product reactant
progress of reaction progress of reaction
Units of H: kJ mol1

ht
Note: “per mole” in the unit of H implies per stoichiometric quantities as specified in the balanced
chemical equation.
2 Definitions....
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Hr is the heat change (or enthalpy change) when molar quantities of reactants, as specified in the
chemical equation, react completely to form products under the standard conditions of 298 K
and 1 bar.
Example: CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) Hr = 890 kJ mol–1
2CH4(g) + 4O2(g)  2CO2(g) + 4H2O(l) Hr = 2(890) = 1780 kJ mol–1
Hf is the heat change (or enthalpy change) when 1 mole of substance is formed from its constituent
elements in their standard states under standard condition of 298 K and 1 bar.
3
Example: Na(s) + ½Br2(l) + O2(g)  NaBrO3(s) Hf of NaBrO3(s)
py
2
Hf can be endothermic or exothermic. However, Hf(elements in its standard state) is zero.
Hc is the heat evolved (or enthalpy change) when 1 mole of substance is completely burnt in excess
oxygen under standard condition of 298 K and 1 bar.
Examples: CH3CH2OH(l) + 3O2(g)  2CO2(g) + 3H2O(l) Hc of CH3CH2OH(l)
Mg(s) + ½O2(g)  MgO(s) Hc of Mg(s)
Hc is always exothermic.
Co
Hneut is the heat evolved (or enthalpy change) when 1 mole of water is formed from the reaction of an
acid and an alkali under standard condition of 298 K and 1 bar.
Examples: NaOH(aq) + ½H2SO4(aq)  ½Na2SO4(g) + H2O(l) Hneut
H+(aq) + OH(aq)  H2O(l) Hneut
Hneut is always exothermic and has a value of 57 kJ mol1 for strong acid–strong base reaction.
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 17 Topic 5: Chemical Energetics

Definitions (Continued)....
X)
Enthalpies that form gaseous atoms:
Hat is the heat absorbed (or enthalpy change) when 1 mole of gaseous atoms is formed from the
elements in its standard state under standard condition of 298 K and 1 bar.
Example: ½Br2(l)  Br(g) Hat of Br(g)
Hat is always endothermic.
E(AB) is the heat absorbed (or enthalpy change) when 1 mole of covalent bond between two atoms in
(LT
the gas phase is broken into gaseous atoms under standard condition of 298 K and 1 bar.
Example: Br2(g)  2Br(g) E(Br–Br)
½H2O(g)  ½O(g) + H(g) E(O–H)
E(A–B) is always endothermic.
Enthalpies that form ions:

1st IE is the heat absorbed (or enthalpy change) when 1 mole of electrons is removed from 1 mole of
gaseous atom to form a singly charged cation.
Example: Mg(g)  Mg+(g) + e 1st IE of Mg
IE is always endothermic.
1st EA is the heat evolved (or enthalpy change) when 1 mole of gaseous atoms gains 1 mole of electrons
to form a singly charged anion.
Example: Br(g) + e  Br 1st EA of Br
st
ht
1 EA is always exothermic. However, subsequent EA is endothermic as energy is required to add a
second electrons to an anion due to repulsion between two negatively charged species.
Enthalpies involving ionic compounds:

LE is the heat evolved (or enthalpy change) when 1 mole of ionic compound is formed from its
constituent gaseous ions under standard condition of 298 K and 1 bar.
Example: Mg2+(g) + 2Br(g)  MgBr2(s)
rig
LE of MgBr2(s)
q q
LE is always exothermic and |lattice energy|  which is also a measure of ionic bond strength.
r  r
Hhyd is the heat evolved (or enthalpy change) when 1 mole of gaseous ion is hydrated under standard
condition of 298 K and 1 bar.
Example: Mg2+(g)  Mg2+(aq) Hhyd of Mg2+(g)
charge of ion
Hhyd is always exothermic and |Hhyd|  which is also a measure of the strength of
size of ion
py
ion–dipole interaction formed between ions and water molecule.
Hsoln is the heat change (or enthalpy change) when one mole of substance is completely dissolved in
enough water such that there is no more heat change on adding more water under standard
condition of 298 K and 1 bar.
Example: MgBr2(s)  Mg2+(aq) + 2Br(aq) Hsoln of MgBr2(s)
Hsoln can be endothermic or exothermic.
Marking points for comparing LE: Marking points for comparing Hhyd:
Co
1) Quote formula 1) Quote formula

2) Compare charge and radius of ions 2) Compare charge and radius of ions
[Effect of (q+q) on LE > effect of (r+ + r)] 3) Conclude effect on charge density and hence,
3) conclude on lattice energy (more/less exothermic) strength of ion–dipole interactions formed
4) conclude on Hhyd (more/less exothermic)

3 Experimental Determination of H...
 % efficiency 
X)
   heat change of reaction (q) = msolcsolT + CcalT
 100 
Assuming the transfer of heat is 100 % efficient (i.e. no heat lost to/gained from surrounding), calorimeter does
not absorb heat (i.e. Ccal = 0) and density of solution is 1 g cm 3,
heat change of reaction, q (in Joules) = msolcsolT Strategy:

1) Calculate heat change of reaction (in J), taking into
heat change  in kJ 
H (in kJ mol1) =  consideration % efficiency, Ccal and density of
amount  in mol  solution
(LT
Hr – amount of limiting reagent 2) Calculate amount of relevant chemical based on
Hc – amount of substance burnt the type of H to be determined.
Hneut – amount of water formed
3) Calculate H (“+” for endo & “” for exo)
Hsoln – amount of solute dissolved
T can be measured by either measuring Tinitial and Tfinal (i.e. uncorrected T) of the reaction mixture or
measuring T of the reaction mixture over time at a fixed interval (i.e. heating/cooling curve  corrected T).
corrected T f
Ti
uncorrected Tf
uncorrected T corrected T corrected T

uncorrected T
uncorrected Tf
corrected T f
ht Ti
4 Discrepancies between actual data and theoretical value...

rig
 E(A–B)  bond energies in Data Booklet are average values derived from a full range of molecule
containing that particular bond.
 reactants and/or products are not in gaseous state and hence, Hvap and/or Hfus
is not accounted for.
 ring strain in the 3/4membered ring causes angle strain and weaken the bond.
 Hneut  (only if weak acid and/or weak base is involved)
Ionisation of acid/base is endothermic. Some heat evolved from the neutralisation is
absorbed to further ionise the unionised weak acid/base completely. Hence, Hneut is less
exothermic than 57 kJ mol1 for reaction involving weak acid/base.
 LE The compound is not 100 % purely ionic as there is some degree of covalent character in
py
the ionic compound due to polarisation (high charge density of cation and large size of anion).
 q = mcT (if correction curve not done) Heat is gained from/lost to the surrounding and/or calorimeter.
(if correction curve is done) Stirring is not constant.
5 Hess’ Law and Energy Cycle/Level diagram...

Hess’ Law states that the enthalpy change accompanying a chemical reaction is a constant regardless of
the route by which the chemical change occurs, provided that the initial and final states are the same.
Consider the two energy cycles for the reaction A + B  C shown below,
Co
By Hess’ Law, H = H1 + H2 By Hess’ Law, H1 = (H3 + H4)  H5

Key marking points for energy cycle: Key marking points for energy level diagram:
a) all equations balanced with state symbols a) all equations balanced with state symbols
X)
b) correct arrow directions based on H given b) correct arrow directions based on H given and
c) correct H values/symbols with appropriate  (endo) and  (exo)
multiplier c) correct H values/symbols with appropriate
multiplier
d) “+ e” required for equations involving IE and EA
e) “0” required for energy level of elements in
standard state.
(LT
Calculate H using energy cycle Calculate H using formula
(a) All data given are Hf: (a) All data given are Hf:
H = aiHf(products)  aiHf(reactants)
(b) All data given are Hc: (b) All data given are Hc:
H = aiHc(reactants)  aiHc(products)
ht
(c) All data given are BE: (c) All data given are BE:
rig
H = E(reactants)  E(products)
(d) Born–Haber cycle: (for ionic compounds) (d) Born–Haber cycle: (for ionic compounds)
Hf = [Hat (or BE)] + (IE + EA) + (LE)
elements elements gaseous gaseous

py
  atoms ions
ionic cpd gaseous  
atoms gaseous ionic cpd
ions
(e) Hsoln, Hhyd and LE: (for ionic compounds) (e) Hsoln, Hhyd & LE: (for ionic compounds)
Using MX2(s) as an example
Hsoln = (LE) + Hhyd
Co
ionic cpd ionic cpd gaseous

  ions
aq ions gaseous 
ions aq ions

6 Entropy (S) and Entropy change (S)...
Entropy, S, is the measure of disorderliness in a system. The more disordered a system, the larger its
X)
entropy value.
S = Sfinal – Sinitial
 S > 0 (i.e.Sfinal > Sinitial)  increase in disorderliness
S < 0 (i.e.Sfinal < Sinitial)  decrease in disorderliness
Note: Like H, S depends only on the initial and final states of the system and is independent of the reaction
pathway taken (i.e. Hess’ Law applies).
Also, entropy S is always a positive value! However, it is S that can be negative/positive depending on
(LT
the change in the disorderliness of the system!
Factors affecting entropy (S) (and hence, sign of S): Marking points for explaining sign of S:
(a) sign of S
(b) increase/decrease of disorderliness
 Temperature (e.g. Cl2(g) at 298 K  Cl2(g) at 373 K) (c) explain using relevant factor affecting S
S > 0 as there is an increase in disorderliness of the system since an increase in temperature
increases the kinetic energy of molecules, resulting in a broadening of the Boltzmann energy
distribution and more ways of arranging energy quanta in the hotter gas.
 Phase change (e.g. Br2(g)  Br2(l))

S < 0 as there is a decrease in disorderliness of the system since the system changes from a more
ht
disordered gaseous state to a more ordered liquid state.
 No. of gaseous/aqueous particles (e.g. Br2(g)  2Br) (gas particles takes priority)
S > 0 as there is an increase in disorderliness of the system since the reaction proceeds with an
increase in amount/number of gas particles from 1 mol to 2 mol.
e.g. [Cr(H2O)6]3+ + 3en  [Cr(en)3]3+ + 6H2O

rig
S > 0 as there is an increase in disorderliness of the system since the reaction proceeds with an
increase in amount/number of particles from 4 mol to 7 mol.
 Mixing (e.g. 1 mol of Cl2(g) at 298 K added to 1 mol of N2(g) at 298 K)

S > 0 as there is an increase in disorderliness of the system since mixing results in a more disordered
arrangement of molecules.
 Change in volume of gas (e.g. Ar at 2 atm  Ar at 1 atm)

S > 0 as there is an increase in disorderliness of the system since the decrease in pressure results in
an increase in volume and hence, the particles have less ways of arrangement.
py
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7 Thermodynamic Feasibility (G)...
X)
(LT
G = H  TS Forward reaction is Forward reaction is
energetically feasible NOT energetically feasible
Units of G is kJ mol1 (Rf > Rb) (Rf < Rb)
H is kJ mol1
S is J mol1 K1 G < 0 G = 0 G > 0
T is in K Reaction is at equilibrium
(Rf = Rb)
Example: phase change
 Effect of Temperature on G and G

ht
Assuming H and S do not change with temperature (which may not always be valid), some reaction can be
made energetically feasible by either lowering or increasing the temperature.
Marking point: Example: H2O(l)  H2O(g) H > 0 and S > 0

a) Do curly brackets on G = H  TS G  H T S
b) State how TS changes with temperature  ve  ve
c) Determine sign of G by comparing |H|  ve
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with |TS| When temperature increases, TS becomes more
d) Conclude spontaneity at high/low/all negative.
temperature. At high enough temperature, G < 0 since |H| < |TS|.
Hence, the reaction is spontaneous at high temperature.
8 Further reading on Hsoln and Ssoln...

Quantitative Qualitative
Hsoln   LE   Hhyd (|Hhyd|) Energy released upon forming ion–

 ve
 ve
dipole interaction between ions and H2O
 ve molecules is (>) more than sufficient to
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 Hsoln > 0 (not soluble) when |LE| > |Hhyd| compensate the (|LE|) energy required to break
 Hsoln < 0 (soluble) when |LE| < |Hhyd| the strong ionic bonds between ions.
Hence, the substance is soluble in water (Hsoln < 0).
Ssoln  Ssolute  Ssolvent Ssoln > 0 as there is an overall increase in the
 ve  ve
disorderliness since the (|Ssolute|) increase in
disorderliness when the ordered ionic lattice is
 Ssoln > 0 when |Ssolute| > |Ssolvent|
broken into free ion is greater than the (|Ssolvent|)
 Ssoln < 0 when |Ssolute| < |Ssolvent| decrease in the disorderliness when the solvent
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molecules arrange themselves around ions.

Topic 6: Reaction Kinetics
X)
1 Definition 1: Rate of reaction is the change in concentration of reactants or products per unit time.
For a reaction: A + B  C
d A d B d C
rate =  =  =+ [Note: Rate is always positive!!]
dt dt dt
 Rate at a particular instant = |gradient of tangent at a point| of curve in a concentration–time graph
(LT
(i.e. initial rate = magnitude of gradient of tangent at t=0)
 Usual units of rate are mol dm–3 s–1, mol dm–3 min–1
 [reactant] decreases and [product] increases with time
[A] or [B] / mol dm –3 [C] / mol dm –3
gradient of tangent at time t1 | gradient of tangent at t=0 |

= instantaneous rate at t1 = initial rate

0 t/s t/s
t1
Fig 1.1
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Concentration of reactant A or B vs time
0
Fig 1.2 Concentration of product C vs time
Definition 2: Rate equation is an experimentally determined mathematical expression of reaction rate in

terms of concentration of reactants.
Definition 3: In an experimentally determined rate equation: Rate = k[A]m[B]n, where A and B are the
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reactants, order of reaction is (m+n).
Note: Order of reaction ≠ stoichiometric number of overall equation!!!

It must be deduced from experimental data!
Definition 4: Rate constant, k, is the proportionality constant in an experimentally determined rate

equation, Rate = k[A]m[B]n.
Note: Units of k depends on the overall order of reaction (i.e. can give clue on overall order of reaction!)
Value of k depends on temperature and activation energy Ea (i.e. catalyst).
When value of k increases, rate of reaction increases.
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Ea
 Ea
Arrhenius equation: k = Ae RT
(or lnk = lnA  ) (i.e. k  with Ea and  T)
RT
Definition 5: Half–life (t½) is the time taken for the concentration/amount of reactant to reduce to half of
its original concentration/amount.
Note: Only first order reactions have constant half–lives!! The same applies for quarter–life etc (e.g t¼, t¾,
t10%).
n
initial amount  1 

final amount  2 
where n is the no. of half–lives passed.
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2019 JPJC J2 H2 Chemistry (9729) / LeeTX 23 Topic 6: Reaction Kinetics

2 Determination of Order of Reactions : Graphical Methods (Summary) d A d C
rate =  =+
For a general reaction A + B  C , Rate = k[A]m [B]n = k’ [A]m (or rate = k(pA)m) where k’ = k[B]n = constant (i.e. [B] is kept constant) dt dt
Order of reaction Zero order (m = 0) First order (m = 1) Second order (m = 2)
T
w.r.t. [A] (or pA) rate is independent of [A] Rate  [A] Rate  [A]2
dA dA
rate =  d  A  = k’ Rate =  = k’[A] Rate =  = k’[A]2
Rate equation dt dt dt
Units of k = mol dm–3 s–1 Units of k = s–1 Units of k = mol–1 dm3 s–1
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[A] /mol dm–3 [A] /mol dm–3 [C] /mol dm–3 [A] /mol dm–3
Conc vs time [C]max
(
k’ = |grad| = rate [A]o (t½)1 = (t½)2 [A]o
graph ¾[C]max (t½)1 ≠ (t½)2
½[C]max
½[A]o 0.5[A]o
Rate at t1
¼[A]o 0.25[A]o
= |Gradient of
t
tangent at t1| 0 t /s t /s 0 (t½)1 (t½)2 t /s 0 (t½) (t½)2
t /s
0 (t½)1 (t½)2
1
= dA ln 2
dt Half–life (t½) is not constant. half–life is constant (t½ = where k’ is the rate Half–life (t½) is not constant.
k'
constant of an overall first order reaction)
h
Using rate = k’, Using rate = k’[A] Using rate = k’[A]2
rateconc. of
reactant graph rate /mol dm–3 s–1 rate /mol dm–3 s–1
rate /mol dm–3 s–1 rate /mol dm–3 s–1
n
rate  [A] rate = k’ [A]2
yaxis = rate
xaxis = [A]
(0,0)
(or [A]n)
*must start from
Graph to plot in
k’
1. [A] against time

[A] /mol dm
 straight line with

–3
r ig
1. [A] against time
0
 curve with constant t½

k’ = |grad|
[A] /mol dm –3 0
k’ = |grad|
2
[A] /mol dm
1. Rate against [A]2

2 –6
4y
y
0
 straight line with positive gradient, passing

x
2x
[A] /mol dm–3
negative gradient (Show working on graph) through origin.

order to determine
2. Rate against [A] y 2. Rate against [A] 2. Rate against [A]2
order of rxn w.r.t
to [reactant]  horizontal line  straight line with +ve gradient, passing through  upward sloping curve such that when [A] is
origin doubled, the rate is quadrupled.
p (Show working on graph)

3 Pseudo–first order reaction is one which is not truly first order but show a first order kinetics under
X)
special conditions.
e.g. Rate = k[A]m [B]n, if [B] >> [A], only a small fraction of B reacted such that [B] is approximately
constant during reaction, the rate equation is simplified as rate = k’ [A]m where k’ = k[B]n) (i.e. pseudo–
mth order).
Circumstances where [B] >> [A] or kept constant,
 B is added in large excess or B is a solvent
 B is a solid or catalyst
ln 2 ln 2
(LT
 If m = 1 (i.e. pseudo–first order reaction), t 1 of A   and t½ of A depends on [B] (n  0).
k B
n
2
k'
4 Elementary reaction is a reaction that proceeds in a single step and cannot be broken down into simpler
steps.
Note: Since an elementary reaction has ONLY ONE single step, the order of reaction w.r.t the reactants is
indicated by the stoichiometric ratio of the reactants.
Most reactions are believed to take place in a series of steps known as reaction mechanism.
The mechanism for a chemical reaction is usually proposed on the basis of experimentally determined
reaction rate data and also on experimental detection of short-lived species (known as reaction
intermediates) which are NOT represented in the stoichiometric equation.
Definition 6: Rate determining step is the slowest step in the multi–step process of a reaction and it
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determines the rate of reaction. It is the step with the largest Ea.
Definition 7: Activation energy Ea is the minimum energy that a reactant must have for reaction to occur.
 Rate equation indicates the number & type of reactants involved in the r.d.s (slow) of the mechanism.
e.g. rate = k [CH3CH2Br][OH–]  the r.d.s (slow step) involves one molecule of CH3CH2Br and one ion of OH–.
Note: Intermediate should not appear in the rate equation. If the slow step involves an intermediate,
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[intermediate] should be expressed in terms of [reactant].
5 Energy Profile (Diagram) of a Reaction

Consider the reaction: A + 2B  C, Hr < 0
energy /kJ mol–1
transition states
Ea,1
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Ea,2
intermediate
reactant
Hr
product
progress of reaction

 forward backward 
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Forward reaction (A + 2B  C, Hr < 0) Checklist for energy profile diagram:

Step 1: A + B  AB Ea1 (slow)  2 steps  2 ‘humps’
Step 2: B + AB  C Ea2 (fast)  Step 1 is rds  Ea of reaction (largest)
 Rate = k [A][B]  Exothermic  energy of pdts < energy of reactants
 Ea of the forward reaction is Ea1
 Forward reaction is exothermic
6 Definition 8: Effective collision is when particles collides with energy ≥ Ea and with correct orientation.
X)
Higher the frequency of effective collisions between particles, faster the rate of reaction.
Factors affecting Rate of reaction

(a) Effect of surface Area on rate: (e.g. finely divided solid versus lumps of solid)
 finely divided solid has larger surface area,
 frequency of effective collisions between reactant particles is higher
 rate of reaction is higher
(LT
(b) Effect of concentration of reactant on rate
 When [reactant] increases, there is more reactant per unit volume
 frequency of effective collision between reactant particles is higher
(c) Effect of pressure of gaseous reaction on rate

 When the pressure of vessel increases, the gas particles are forced closer together
 frequency of effective collision between reactant particles is higher
Note: When volume of vessel increase, the total pressure of system decreases.
(d) Effect of temperature on rate ht

number of particles
T2 > T1
T1
no. of particles with energy ≥ Ea at T 2
T2
no. of particles with energy ≥ Ea at T 1
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0 Ea energy
[Note: Boltzmann distribution graph shifts only when temperature change.]
 When temperature increases from T 1 to T2, the average kinetic energy of particle increases and
hence, the number of particles with energy ≥ Ea increases
 frequency of effective collision between reactant particles with energy ≥ Ea increases,
 rate of reaction increases (largely).
(e) Effect of catalyst on rate

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number of particles
no. of particles with energy ≥ Ea’ for catalysed reaction
no. of particles with energy ≥ Ea for uncatalysed reaction

Ea : activation energy of uncatalysed reaction
Ea,cat : activation energy of catalysed reaction
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0
Ea,cat Ea energy
Note: Since there is no change in temperature, Boltzmann distribution graph will not shift.
 A catalyst provides an alternative reaction pathway of lower activation energy (Ea,cat).

 the number of particles with energy ≥ Ea,cat is higher
 frequency of effective collision between reactant particles is higher,
 rate of reaction is higher.
7 Types of catalysis
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(a) Homogeneous catalysis: uses a catalyst that operates in a same phase as reactants and products.
(b) Heterogeneous catalysis: uses a catalyst that operates in a different phase as reactants & products.
Note: For details on (a) and (b), refer to Transition Metals.
(c) Autocatalysis: a reaction is said to be autocatalysed if the product/intermediate can act as a catalyst
for the reaction.
Graph indication of autocatalysis:
(LT
rate [reactant]
[reactant] is
more significant Gradient  implies rate 
[catalyst] is than [catalyst]
([catalyst] is more significant
more significant  rate 
Gradient  implies rate 
than [reactant] [reactant] is more significant
 rate 
time 0 time
0
(d) Biological catalysis: a reaction is said to be biologically catalysed if an enzyme is used to catalyse the
specific biological reaction
Graph indication of biological catalysis:
rate
horizontal  zero order wrt [substrate]
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linear  1st order wrt [substrate]
0 [substrate]
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 When [substrate] is low, the rate is approximately 1st order w.r.t [substrate] as there are still relative
a lot more active site of enzyme available.
 As [substrate] increases, rate is no longer 1st order w.r.t [substrate] as more active sites of
enzyme are occupied by substrate.
 When [substrate] is high, the rate is zero order w.r.t substrate as all active sites of enzyme are
occupied by substrate (i.e. saturation).
8 Methods of Monitoring Rates of Reaction

Non–continuous method: Measuring the time taken to reach an easily seen stage (‘clocked reaction’)
Measure time taken for a fixed change to occur
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1
 (if fixed change is amt of product formed), rate 
time
 (if fixed change is amt of reactant used), rate 

reactant 
time
Note: When [A]original and the total volume of the reaction mixture are kept constant,
volume of reactant A used, VA   A in reaction mixture
e.g. Yellow ppt. of sulfur is formed when S2O32– is reacted with H+.
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After mixing the two reactants, obtain the time for the “Cross” or any printed pattern to be completely
obscured by S(s).
Suitable for : reaction that has some sudden observable change after the reaction progressed
for a certain time
Data collected : time taken for the sudden observable change for different concentrations of one
reactant, keeping other factors constant.

8 Continuous method: Measuring change in physical quantity over time
X)
Examples of physical quantity: volume of gas, mass of reaction mixture, colour intensity, volume of titrant
 Volume of gas formed over time

thread
vol. of CO2(g) /cm3
gas syringe
(LT
small test
tube
CaCO3(s) HCl(aq) 0 time /s

t
Suitable for : reaction that forms gaseous products
Data collected : volume of gaseous product formed
 Mass of reaction mixture over time

cotton wool to trap mass of rxn mixture /g
vaporized soln H2(g) escape
carried by H2  mass loss
mass lost
Mg(s) in = mass of H2 produced
electronic
balance
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50.51
HCl(aq)
0 t time /s
Suitable for : reaction that forms gaseous products

Data collected : mass loss of gaseous products
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 Volume of titrant used over time (sampling, quenching, titration)
Step 1: Drawing of known fixed volumes of solution (aliquots) from reaction mixture at various time, using
pipette (i.e. concentration of reactant/product at various time will be different.)
Step 2: Quench (i.e. stop reaction or slow down significantly) the sample before titration.
 cool mixture rapidly using ice bath or
 add large amount of cold water to dilute and cool mixture or
 add inhibitor to slow down the reaction or
 add known amount of excess reagent to react away one reactant rapidly so that reaction stops at
the precise timing
Step 3: Titrate the sample with suitable titrants using appropriate indicators (if nec.)
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Volume of titrant used  [reactant] left at time t

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Topic 7: Chemical Equilibrium
X)
1
Definitions:
 Reversible reaction is a reaction that may proceed from either direction.
 Dynamic equilibrium is a reversible process at equilibrium in which the rate of forward reaction and
backward reaction are equal.
Characteristics of Dynamic Eqm:
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(1) closed system
(2) reversible process
(3) rate of forward reaction (Rf) = rate of backward reaction (Rb)
(4) no net change in amount of reactants and products (even though the reaction is still occurring)
ht
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2 Le Chatelier’s Principle…
Definition:
Le Chaterlier’s Principle states that if a system in equilibrium is disturbed by a change in conditions,
the position of equilibrium shifts to minimise the effect of the change applied.
Marking point for predicting effect of Some changes in conditions:

change in condition on POE  addition/removal of reactants
* Write and label eqm equation (use “”)  addition/removal of products
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(1) State the change in condition  addition of water for aqueous reactions
(2) Effect on poe   in p (or  in V) for gaseous reactions only
(3) Reason for the shift
  in T (given H)
(4) Conclude
 catalyst
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2019 JPJC J2 H2 Chemistry (9729) / LeeTX 29 Topic 7: Chemical Equilibrium

Effect of changes in conditions on POE & value of K and rate:
rate at which eqm
X)
Change in condition Shift in poe & reason for the shift value of K
is established
right
addition of reactants
(to remove some of reactants added / to unchanged increases
/removal of products
form some of the products removed)
left
addition of products/
(to form some of reactants removed / to unchanged increases
removal of reactants
remove some of the products added)
(LT
in the direction that has more concentration
addition of H2O unchanged decreases
terms.
increase in volume of in the direction that  number of gas

vessel  decrease particles so as to p)
unchanged decreases
in total pressure of no change if both sides of equations have
system the same no. of gas particles
in the direction that favour endothermic  if shift right

increase in reaction so as to absorb some heat  if shift left increase
temperature
no change if H = 0 unchanged
no change since rate of forward and
catalyst backward reaction increase by the same unchanged increases
extent
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Strategy for Deductive question (Given the effect of  in temperature/pressure of the system)
(1) Effect of  in condition  deduce if the poe has shifted left/right
(2) LCP’s response to  in condition  T: fav endo/exo ; p:  or  no. of gas particles
(3) Combine (1) and (2) to conclude.
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(Application of LCP) The Haber Process...
N2(g) + 3H2(g)  2NH3(g) ---(1) H < 0
Optimum Operating Conditions used: 450 °C, 250 atm, finely divided iron
Operating conditions used are often a compromise between yield, cost and rate of reaction.
 Temperature: When temperature decreases, the poe of N2(g) + 3H2(g)  2NH3(g) shifts right to favour
the exothermic reaction so as to release some heat to increase temperature. Hence, the %
yield of NH3 increases.
However, the reaction is slow at low temperature due to low frequency of effective
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collisions. A compromise temperature of 450C is used to achieve reasonably high yield of

ammonia at reasonably high rate.
 Pressure: When pressure increases, the poe of N2(g) + 3H2(g)  2NH3(g) shifts right to reduce
amount of gas particles so as to reduce pressure. Hence, % yield of NH3 increases.
The reaction is fast at higher pressure due to higher frequency of effective collisions
since particles are closer.
However, very high pressure will increase both capital cost and operating cost. A
compromise pressure of 250 atm is used to achieve reasonably high yield at reasonably low
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costs.
 Catalyst: When finely divided Fe is added, the poe of N2(g) + 3H2(g)  2NH3(g) does not shift since
the rate of both forward and backward reaction increase by the same extent. Hence, %
yield of NH3 is not affected.
The reaction is faster since catalyst provides an alternate pathway of lower Ea.

3 Calculations…
X)
Experimentally, it is found that at a constant temperature,
For a reaction: a A(aq) + b B(aq)  c C(aq) + d D(aq)
C  D 
c d

eqm eqm
Kc Units of Kc : (mol dm–3) (c+d–a–b)
 A  B 
a b
eqm eqm
Kc is the equilibrium constant expressed in terms of concentrations and is dependent on temperature

only. If the temperature remains constant, Kc will remain constant.
(LT
Experimentally, it is found that at a constant temperature,
For a reaction a A(g) + b B(g)  c C(g) + d D(g) (For gaseous system only!)
p  p 
c d
Kp  C D
Units of Kp : Pa (c+d–a–b) or (Nm–2) (c+d–a–b) or (atm) (c+d–a–b)
p  p 
A
a
B
b
Kp is the equilibrium constant expressed in terms of partial pressures and is dependent on

temperature only If the temperature remains constant, Kp will remain constant.
Note for Kc and Kp:

(1) Do not include H2O unless reaction is not in (aq) medium and/or [H2O] is given.
(2) Do not include solid as [solid] is a constant.
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(3) Do not include solids and liquid for Kp as they exert little/no pressure to the syst.
(4) Check the units of pressure used in the question.
Useful formulae in calculations

nA
 pA =  ptotal (for calculation of partial pressure of gas A  pA  nA )
ntotal
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 ptotal = pA + pB + pC + … (Dalton’s Law of Partial Pressure)
 pV = nRT (p = pA if n = nA or p = ptotal if n = ntotal )
amt reacted conc. reacted
 % dissociation (or conversion) =  100 % (or  100 %)
initial amt initial conc.
actual yield
 % yield =  100 %
theoretical (or max) yield
Strategy for Equilibrium calculation

(1) Establish ICE Table
py
(2) Input given data to the respective cell

(3) Complete the table by applying mole ratio to calculate the “change”
(4) Substitute values/algebra into Kc and solve!
Note: If equilibrium concentration/pressure/amount of all species are given, go to step 4 directly!
4 Linking G with Q and K...

G (in J mol1) = RT ln K
G tells us the extent of reaction (not rate!), given eqm is already established (i.e. G = 0 and Q = K).
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Sign of G Magnitude of K Inference

G < 0 K >> 1 poe lies on the far right and the forward reaction is essentially complete
G > 0 K << 1 poe lies on the far left and the forward reaction hardly occurs

Topic 8: Galvanic Cells
X)
1 COMPARISON BETWEEN GALVANIC CELL & ELECTROLYTIC CELL...
ELECTROCHEMICAL CELL
Galvanic Cell Electrolytic Cell
chemical energy to electrical energy electrical energy to chemical energy
energy
change (i.e. reaction occurs spontaneously to (i.e. requires an external source to provide
generate current) current to drive the reaction)
(LT
cell
spontaneous non–spontaneous
reaction
polarity of positive electrode
negative electrode where oxidation occurs
anode where oxidation occurs
polarity of negative electrode
positive electrode where reductions occurs
cathode where reductions occurs
electron
anode to cathode anode to cathode
flow
e e e e
V
(+) () ()
(+)
(+) () (+) ()
setup
cathode
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salt bridge
anode anode cathode
electrolyte
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Standard conditions (represented by ‘’) are:

 298 K (or 25 C)
 1 bar for gas
 1 mol dm3 for solution of aqueous ions
2 Definition 1: Standard electrode potential of a half–cell, E, is the relative potential of this
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half–cell under standard conditions as compared with the standard hydrogen

electrode whose E is assigned as zero.
(Also known as standard reduction potential)
Note: If the reference electrode is changed, the value of E changes too.
Definition 2: Standard hydrogen electrode consists of H2 gas at 1 bar bubbling over platinised Pt
electrode which is dipped into 1 mol dm3 H+ solution at 298 K.
2H+(aq) + 2e  H2(g) E(H+/H2) = 0.00 V
Definition 3: Standard cell potential, Ecell, is the electromotive force (e.m.f.) of a galvanic cell which
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consists of two half–cells connected under standard conditions.

The E cell value is the difference between the standard electrode potential (E) of the
two half–cells.
E cell = Ered  Eox
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 32 Topic 8: Galvanic Cells

3 Experimental determination of E and drawing of Galvanic cell setup...
X)
(LT
If one of the half–cell is S.H.E:
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Ecell = Ered  Eox = E of the half–cell
Note: The voltage reading only tells us the value of E of the unknown half–cell.
The sign of E depends on whether the unknown half–cell is [R] or [O] relative to SHE.
 Connect the two half–cells to obtain a positive voltmeter reading (i.e. value of E obtained).
 If the unknown half–cell is connected to positive terminal of voltmeter, it implies that the unknown
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half–cell is the cathode (i.e. reduction). Hence, the sign of E is positive (i.e. more likely to be reduced
than SHE).
If negative terminal, the sign of E is negative (i.e. more likely to be oxidised than SHE).
4 Significance & Applications of E…

By convention, the half–equation for electrode potential is written with reduction as forward reaction:
example: Fe3+(aq) + e  Fe2+(aq) E(Fe3+/Fe2+) = +0.77 V
The value of the electrode potential depends on the position of the redox equilibrium and it can be positive
or negative.
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 More positive E value  position of equilibrium lies more to the right

 reduction is more favoured (i.e. lower O.S is more stable)
 stronger the O.A (LHS) or stronger oxidising power
 More negative E value  position of equilibrium lies more to the left

 oxidation is more favoured. (i.e. higher O.S is more stable)
 stronger the R.A (RHS) or stronger the reducing power
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If the electrode potential is not measured under standard conditions, it will be written as E(Fe3+/Fe2+) and
the value will deviate from E (i.e. apply LCP)
 change in concentration/pressure of species (addition or removal or dilution)
 change in total pressure (for gaseous system)
 change in temperature
 nature of metal

5 Significance & Applications of Ecell…
Ecell can be used to determine:
X)
(a) the voltage of a galvanic cell (i.e. battery)  Ecell always > 0!
(b) thermodynamic feasibility of a redox reaction (i.e. mixing)  Ecell can be +ve, ve, 0
E cell = Ered  Eox Gr = nFE cell

where n = number of e transferred per mol redox equation during the redox, and
1 
F = Faraday’s constant (96500 C mol , i.e. charge passed per mole of e )
(LT
Strategy to solve Ecell calculation: Interpretation of Ecell:
(1) Determine what species are present  Ecell > 0 (i.e. G < 0)
(2) Quote the relevant halfequations & E value  forward reaction is energetically feasible
(Check if there is at least a pair of RA & OA first)  Use “” in overall equation
(3) Determine [O] & [R]  Ecell < 0 (i.e. G > 0)
 Galvanic cell setup: Compare E  forward reaction is not energetically feasible
 Mixing: Circle the species present  No overall equation
(4) Calculate Ecell
 Ecell = 0 (i.e. G = 0)
 reaction is at equilibrium (Rf = Rb)
 Use “” in overall equation
Note:
(1) Do not consider H2O as reactant for galvanic question unless otherwise stated!
ht
(2) Ignore spectator ions (e.g. Na+, SO42) unless otherwise stated!
(3) Use E(Cu2+/Cu) if question involves Cu2+ or Cu unless otherwise stated!
(4) Use E(MnO4/Mn2+) for MnO4 in acidic medium.
(5) H2O2 can act as either a R.A or an O.A.
K
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G = RT lnK RT
Ecell = lnK
nF
Thermodynamic where R = gas constant = 8.31 J mol1 K1
Feasibility T = absolute temperature (in K)
n = amount of electrons transferred
G Ecell F = Faraday constant = 96500 C mol 1
= H  TS G = nFE
 
cell = Ered  Eox G = Gibbs free energy change (in J mol 1)
Limitations of E and Ecell…

(1) Did not account for kinetic feasibility (slow due to high Ea)
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Examples:
 The reaction between I and S2O82 is energetically feasible (Ecell = +1.47 V >0). However, in actual fact,
the reaction does not occur.
The reaction is slow due to high Ea since there is repulsion between the two negatively charged ions.
 The reaction between Cu and H+ is energetically feasible (Ecell = +0.34 V >0). However, in actual fact,
the reaction does not occur.
The reaction is slow due to high Ea since the H–H covalent bond is very strong.
(2) Valid only if under standard condition (Ecell may be more/less positive than predicted)
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Apply Le Chatelier’s Principle to predict how E and Ecell will change.

Example:
 The reaction between MnO2 and conc. HCl is not energetically feasible (Ecell = <0). However, in actual
fact, the reaction does occur.
 Higher [Cl] shifts the position of equilibrium of Cl2 + 2e  2Cl to the left, making E(Cl2/Cl) more
negative than +1.36 V. Hence, Ecell becomes more positive than 0.13 V.
 Higher [H+] shifts the position of equilibrium of MnO2 + 4H+ + 2e  Mn2+ + 2H2O to the right, making
E(MnO2/Mn2+) more positive than +1.23 V. Hence, Ecell becomes more positive than 0.13 V.

6 Hydrogen–Oxygen Fuel Cells (Environmentally friendly cell)..
X)
Acidic fuel cell Alkaline fuel cell
species present: H2(g), O2(g), H+(aq) species present: H2(g), O2(g), OH(aq)
2H+ + 2e–  H2 0.00 V ---[O] more –ve 2H2O + 2e–  H2 + 2OH– –0.83 V ---[O] more –ve
O2 + 4H+ + 4e–  2H2O +1.23 V ---[R] more +ve O2 + 2H2O + 4e–  4OH– +0.40 V ---[R] more +ve
Ecell = (+1.23) – (0.00) Ecell = (+0.40) – (–0.83)

= +1.23 V > 0 (energetically feasible) = +1.23 V > 0 (energetically feasible)
(LT
anode : 2H2(g)  4H+(aq) + 4e– anode : 2H2(g) + 4OH–(aq)  4H2O(l) + 4e–
cathode : O2(g) + 4H+(aq) + 4e–  2H2O(l) cathode : O2(g) + 2H2O(l) + 4e–  4OH–(aq)
overall : 2H2(g) + O2(g)  2H2O(l) overall : 2H2(g) + O2(g)  2H2O(l)
ht
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Topic 9: Electrolytic Cells
X)
1 Predicting Products formed in an electrolysis (Qualitative)...
There will be selective reactions at the electrodes which is dependent on:
 Physical state of electrolyte (molten versus)

Negatively charged anion is attracted to and oxidised at the positively charged anode while
positively charged cation is attracted to and reduced at the negatively charged cathode.
(LT
Note: If in aqueous phase, to consider water and compare E
 Position of species in the redox series(electrode potential)

more positive E  position of equilibrium lies more to the right
 species on LHS is more readily reduced
more negative E  position of equilibrium lies more to the left
 species on RHS is more readily oxidised
 Concentration of aqueous electrolyte (dilute versus concentrated) – Le Chatelier’s Principle

Use LCP to determine how the position of equlibrium will shift and hence, how E value changes.
 Nature of electrode (reactive versus inert electrode) – use E values
To consider the reactive metal for oxidation at anode.
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Note: Unless otherwise stated, NO3, SO42 and Group 1 ions are usually not oxidised.
Strategy to solve Qualitative Electrolysis

Step 1: Identify all species present at anode and at cathode
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Anode : anion, water and metal
Cathode : cation and water
Step 2: Determine species that is reduced and oxidised
 Only 1 species for the electrode: oppositely charged species attract.
 More than 1 species for the electrode: use E to predict the species that is reduced/oxidised.
Anode : Species on RHS and most negative E
Cathode : Species on LHS and most positive E
Presentation of Answer
At anode, is more easily oxidised than as E ( ) is more negative than E ( ).
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At cathode, is more easily reduced than as E( ) is more positive than E ( ).

* Always use “” for writing equation for electrode reaction/ion–electron equation.
Note: If the anode is a reactive metal (e.g. Cu) is oxidised, consider its corresponding cation (e.g. Cu 2+) for
possible reduction at the cathode.
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2019 JPJC J2 H2 Chemistry (9729) / LeeTX 36 Topic 9: Electrolytic Cells

2 Calculating amount of Products formed in an electrolysis (Quantitative)
Q : electric charge in coulomb (C)
X)
ne : amount of electrons passed through circuit (mol)
I : current in ampere (A)
Q = It = neF t : time in seconds (s)
where (F = Le) F : Faraday constant (96500 C mol1)
L : Avogadro constant (6.02  1023 mol1)
e : charge of one electron (1.60  1019 C)
(LT
Mx+ + xe  M(s)
By comparing ne and n(M) formed, the value of x can be determined.
Since Q = It = neF, the amount of product is dependent only on current (I) and time
taken (t) during electrolysis. Any other factors such as change in concentration of
electrolyte does not affect the amount of products formed.
m2 I2  t 2
mass or volume of product formed  total charge Q (= I  t) (i.e. = )
m1 I1  t 1
When two electrolytic cells (e.g. cell A and cell B) are connected in series,
ne passed in cell A = ne passed in cell B
3 Industrial Applications of Electrolysis...

 Page 16 of notes Anodising of Aluminium
 Page 18 of notes Electroplating

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 Page 17 of notes Purification of Copper
(to increase the protective Al2O3 layer on Al metal)
(to extract pure Cu from copper–containing alloy)
(to coat an object with the desired metal)
 Page 19 of notes Electrolysis of Brine (to produce Cl2 and NaOH used in bleach industry)
Note: There is no need to memorise how each industrial application works as long as you understand and
are able to predict qualitatively the products formed during an electrolysis!
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For each application, you need to know:
(1) purpose
(2) essential components of setup
(3) draw setup
(4) electrode reaction equation
 Anodising of Aluminium
Purpose : increase thickness of corrosion–resistant Al2O3
layer on surface of Al metal
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Electrodes : Al anode, Pt/graphite cathode

Electrolyte : dilute H2SO4(aq)
Species present: H+, SO42, H2O and Al
cathode : 2H+(aq) + 2e  H2(g)

anode : Al(s)  Al3+(aq) + 3e
2Al3+(aq) + 3H2O(l)  Al2O3(s) + 6H+(aq) (Note: 1Al2O3  2Al3+  6e)
Overall : 2Al(s) + 3H2O(l)  Al2O3(s) + 3H2(g)
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 Purification of Copper
Purpose : to extract pure copper from crude copper anode
X)
and deposit it on pure copper cathode
Electrodes : impure Cu anode (containing impurities like
Zn & Ag) and pure Cu cathode
Electrolyte : dilute CuSO4(aq)
Species present: Cu2+, SO42, H2O, Cu, Zn and Ag
At the anode (consider Cu, Zn, Ag and H2O): Cu(s)  Cu2+(aq) + 2e–
(LT
Cu is more easily oxidised than H2O as E (Cu2+/Cu) is more negative than E(O2/H2O).
Zn is oxidised to Zn2+ as E(Zn2+/Zn) is more negative than E (Cu2+/Cu).
Ag is not oxidised as E (Ag+/Ag) is more positive than E (Cu2+/Cu) and is collected as ‘anode
sludge’.
At the cathode (consider Cu2+, Zn2+ and H2O): Cu2+(aq) + 2e–  Cu(s)
Cu2+ is more easily reduced than H2O as E (Cu2+/Cu) is more positive than E(H2O/H2).
Zn2+ is not reduced as E(Zn2+/Zn) is less positive than E (Cu2+/Cu) and Zn2+ remains in solution.
 Electroplating
Purpose : to coat an object with a metal M (e.g. Ag)
ht Electrodes : metal M anode & object to be plated as
cathode
Electrolyte : dilute Mx+(aq)
Species present: Mx+, H2O, M
anode : M(s)  Mx+(aq) + xe

cathode : Mx+(aq) + xe  M(s)
Note: The overall change is the transfer of desired metal from anode to cathode.
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TOPIC 16: Acid, Base and Solubility Equilibria
X)
1 Definitions:
 Bronsted acid is a proton H+ donor. (Note: H+ is equivalent to H3O+.)
Bronsted base is a proton H+ acceptor.
 Define pH : pH = –log10[H+] (i.e. [H+] = 10pH)

Define pOH : pOH = –log10[OH–]
(LT
Define pKw : pKw = pH + pOH ( = 14 at 25 C only)
(Note: pH is a measure of [H+]. It does not relate to strength of acid or base.)
 Conjugate acid–base pair is a pair of compounds which differs from each other by a H+.
Examples:
CH3COOH(aq) + H2O(l)  CH3COO‒(aq) + H3O+(aq)
acid base conj. base of conj. acid
CH3COOH of H2O
NH3(aq) + H2O(l)  NH4+(aq) + OH(aq)
base acid conj. acid conj. base
of NH3 of H2O
H3 O   A  
 Define Ka : K a   ( HA(aq) + H2O(l)  H3O+(aq) + A(aq) )
HA 
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OH  BH 
Define Kb : Kb   ( B(aq) + H2O(l)  OH(aq) + BH+(aq) )
 
B
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For conjugate acidbase pair only: Kw = Ka  Kb (i.e. pKw = pKa + pKb).
 Buffer is a solution which resists pH change when small amount of acid or base is added to it.
(Note: A buffer solution is made up of weak acid and its conjugate base (i.e. salt) or weak base and
its conjugate acid (i.e. salt).)
2 Self–Ionisation of water: 2H2O(l)  H3O+(aq) + OH–(aq) ∆H > 0 ---(1)

At 25 C, Kw = [H3O+][OH(aq)] = 1.00  1014 mol2 dm6
pKw = pH + pOH = 14
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Kw is an equilibrium constant and its value (and hence, pKw) depends on temperature only.
When temperature increases, poe in (1) shifts right to favour endothermic reaction so as to
absorb some heat. Hence, the value of Kw increases with increasing temperature.
Note: pH of water/neutral solution = 7 only at 25 C.
3 Type of system: strong acid Type of system: strong base

(Examples: HCl, HNO3, H2SO4) (Examples: NaOH, KOH, Ca(OH)2)
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Strong acid ionises completely in H2O to give H+. Strong base ionises completely in H2O to give
HA(aq) + H2O(l)  A–(aq) + H3O+(aq) OH.
B(aq) + H2O(l)  BH+(aq) + OH–(aq)
To prove that an acid is a strong monobasic To prove that a base is a strong monoprotic
acid, show that [H3O+] = [HA]. base, show that [OH] = [B].
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 39 Topic 16: Acids, Bases & Solubility Equilibria
4 Type of system: weak acid Type of system: weak base
(Examples: RCOOH, organic acid or if Ka given) (Examples: NH3, amine or if Kb given)
X)
Weak acid ionises partially in water to give H+. Weak base ionises partially in water to give OH.
HA(aq) + H2O(l)  A–(aq) + H3O+(aq) B(aq) + H2O(l)  BH+(aq) + OH–(aq)
∆H > 0 ---(2) ∆H > 0 ---(3)
To prove that an acid is a weak monobasic To prove that a base is a weak monoprotic
acid, show that [H3O+] << [HA]. base, show that [OH] << [B].
(LT
For a weak monobasic acid, For a weak monoprotic base,
HA + H2O  H3O+ + A B + H2O  OH + BH+
Initial ca  0 0 Initial cb  0 0
Change x  +x +x Change x  +x +x
Eqm ca  x  x x Eqm cb  x  x x
H3O   A   x2 BH  OH 

Ka =  = Kb = =
x2
HA  ca  x B cb  x
x2 x2
Assuming x << ca, Ka  Assuming x << cb, Kb 
ca cb
[H3O+] , x = c a  Ka [OH] , x = c b  Kb
pH = log10[H3O ]
ht +
pH = 14  (log10[OH])
Note:
Ka and Kb are equilibrium constants and their values (and hence, pKa and pKb) depend on
temperature only.
When temperature increases, poe in (2) (or (3)) shifts right to favour endothermic reaction so as to
absorb some heat. Hence, the value of Ka (or Kb) increases with increasing temperature.
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5 Type of system: acidic salt (SA + WB  AS) Type of system: basic salt (WA + SB  BS)
(Example: HCl + NH3  NH4+Cl) (Example: CH3COOH + NaOH  CH3COONa + H2O)
In the salt, the conjugate acid of the weak base In the salt, the conjugate base of the weak acid
(e.g. NH4+) hydrolyses slightly in water to give (e.g. CH3COO) hydrolyses slightly in water to
H3O+. give OH.
BH+(aq) + H2O(l)  B(aq) + H3O+(aq) A–(aq) + H2O(l)  HA(aq) + OH–(aq)
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Given Kb of the weak base that forms the salt, Given Ka of the weak acid that forms the salt,
BH+ + H2O  H3O+ + B A + H2O  OH + HA
Initial cas  0 0 Initial cbs  0 0
Eqm cas  x  x x Eqm cbs  x  x x
Kw H3 O  B  x2 K HA  OH  x2

Ka = = = Kb = w = =
Kb BH  c as  x Ka  A   c bs  x
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Kw x2 Kw x2
Assuming x << cas,  Assuming x << cbs, 
Kb c as Ka c bs
Kw Kw
[H3O+] , x = c as  [OH] , x = c bs 
Kb Ka
pH = log10[H3O+] pH = 14  (log10[OH])
6 Type of system: acidic buffer (WA + its CB) Type of system: basic buffer (WB + its CA)
(Example: Solution with CH3COOH & CH3COONa) (Example: Solution with NH3 and NH4Cl)
X)
HA(aq) + H2O(l)  A–(aq) + H3O+(aq) B(aq) + H2O(l)  BH+(aq) + OH–(aq)
weak conj. base weak conj. acid
acid of HA base of B
When small amount of H+ is added: When small amount of H+ is added:

H+(aq) + A–(aq)  HA(aq) H+(aq) + B(aq)  BH+(aq)
(LT
When small amount of OH– is added: When small amount of OH– is added:
OH–(aq) + HA(aq)  A–(aq) + H2O(l) OH–(aq) + BH+(aq)  B(aq) + H2O(l)
HA + H2O  H3O+ + A B + H2O  OH + BH+

Initial ca  0 cbs Initial cb  0 cas
Eqm ca  x  x cbs + x Eqm cb  x  x cas + x
H3O   A    c bs  x  x  BH  OH   c as  x  x 

Ka = = Kb = =
HA  ca  x B cb  x
c bs  x  c as  x 
Assuming x << ca and x << cbs , Ka  Assuming x << cb and x << cas , Kb 
ca cb
[H3O+] , x =
c a  Ka
ht [OH] , x =
c b  Kb
c bs c as
 pH  pK a  lg
 salt   pOH  pKb  lg
 salt  (i.e. pH = 14 – pOH)
acid base
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At maximum buffering capacity (i.e. solution At maximum buffering capacity (i.e. solution
best resists pH change), [acid] = [salt]. best resists pH change), [base] = [salt].
Hence, pH = pKa. Hence, pOH = pKb.
Volume at which max. buffering capacity occurs Volume at which max. buffering capacity occurs
is ½Veq (if buffer is formed before equiv. point) is ½Veq (if buffer is formed before equiv. point)
or 2Veq (if buffer is formed after equiv. point). or 2Veq (if buffer is formed after equiv. point).
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Steps for sketching a pH titration curve:
Using a titration of CH3COOH (WA in conical flask) against NaOH (SB in burette) as an example.
X)
1. Divided the graph into 4 portions: pH
 draw a dotted line at the end–point on the x–axis (calculate Vneut)
 draw a dotted line at pH = 7 on the y–axis
7
Note:
 x–axis measures the volume of titrant added from burette
 y–axis measures the pH of solution mixture in conical flask 0
Vneut vol /cm3
(LT
2. Mark the initial pH on y–axis. (system: SA/SB/WA/WB) pH
 Determine the initial pH of the solution in the conical flask
(e.g. CH3COOH is titrated with/against NaOH(aq).The calculated initial 7

pH of CH3COOH = 2.5)
2.5 ×
0
Vneut vol /cm3
3. Draw the sharp change in pH at equivalence point. pH
(System: Acidic/Basic/Neutral Salt)
10 Equivalence
Mark the pH of resulting salt solution at equivalence point at the ×point
7 (pH of salt)
centre of sharp pH change.
2.5 ×
ht
SA–SB or SB–SA : pH 3 to 10 (neutral salt) (MO/Ph/BTB)
WA–SB or SB–WA : pH 7 to 10 (basic salt) (Ph/BTB)
0
Vneut vol /cm3
SA–WB or WB–SA : pH 3 to 7 (acidic salt (MO)

(e.g. CH3COOH (WA) + NaOH (SB)  sharp  from pH 7 to 10)
4. Check and mark the buffer region (i.e. mixture of WA/WB and its
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conjugate salt (system: acidic/basic buffer)
pH
The shape of the curve in the buffer region is as follows:
10
× equivalence
7 point
Titrate with base Titrate with acid
(pH↑) (pH↓) 2.5 ×
 WASB titration: buffer region occurs before equivalence point 0
(e.g. acidic CH3COOH/CH3COO–Na+ buffer before end–point for titration of Vneut vol /cm3
CH3COOH against NaOH)
 SBWA titration: buffer region occurs after equivalence point
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 WBSA titration: buffer region occurs before equivalence point

 SAWB titration: buffer region occurs after equivalence point
 Indicate max buffering capacity!
5. The curve levels off at the pH of reagent in the burette. pH

(e.g. curve levels of at pH of NaOH)
10
× equivalence
7 point
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2.5 ×
0
Vneut vol /cm3
7 Solubility of a substance is the maximum amount of the substance dissolved in a given volume
of a particular solvent at a specified temperature.
X)
AmBn(s)  mAn+(aq) + nBm(aq)
Eqm [An+] and [Bm] in saturated solution are called solubility.
Units of solubility can be g dm–3, mol dm–3, etc.
Ksp of AmBn = [An+]m [Bm]n Unit of Ksp is mol(m+n) dm–3(m+n)

Ksp is an equilibrium constant called solubility product & its value depends on temperature only.
Note: For salt with the same total no. of ions (e.g. Ag2CO3 and PbBr2), the value of Ksp is an
(LT
indication of which salt is more soluble in water. If the total no. of ions are different, calculate
the equilibrium concentration of the ions (i.e solubility) to determine which salt is more soluble.
8 Reduced solubility due to Common ion effect (LCP) : e.g. CaF2(s)  Ca2+(aq) + 2F(aq) ---(4)
Presence of common ion, Ca2+(aq) from Ca(NO3)2 causes the poe in (4) to shift to the left,
Hence, the solubility of CaF2 in Ca(NO3)2 is lower than that in water.
Increased solubility due to Complex Formation:

AgX(s) ⇌ Ag+(aq) + X(aq) ---(5)
When NH3(aq) is added, [Ag(NH3)2]+ complex is formed and hence, [Ag+(aq)] decreases and
causes the poe in (5) to shift right, increasing the solubility of AgX.
 Solubility of all AgX(s) is higher in NH3(aq) than in pure water.
ht
Since Ksp of AgCl > AgBr > AgI, the solubility of AgCl in NH3(aq) > AgBr > AgI.
Hence, AgCl completely dissolves in NH3(aq) whereas AgBr partially dissolves in NH3(aq) and AgI
still remain essentially insoluble in NH3(aq).
9 Predicting Precipitation (LCP)

 Condition for Precipitation to occur
rig
If Ionic Product (at the instant of mixing) is
less than Ksp equal to Ksp more than Ksp
Type of solution at
Unsaturated saturated supersaturated
the instant of mixing
precipitation first trace of precipitation
Prediction does not occur precipitation occurs
occurs until IP = Ksp
Note: Ionic product and Ksp have the same expression but the conc. terms in ionic product refer to
ions in any given solution while that in Ksp refer to ions in saturated solution.
Note: When mixing two volumes, dilution occurs. Recalculate the concentration using c1V1 = c2V2
py
 Minimum concentration needed for precipitation to occur (use IP = Ksp)

 Selective precipitation
Calculate the minimum concentration needed to precipitate each salt:
Co
strong acid–strong base  neutral salt strong base–strong acid  neutral salt
X)
(LT
strong acid–weak base  acidic salt weak base–strong acid  acidic salt
ht
rig
weak acid–strong base  basic salt strong base–weak acid  basic salt
py
Co
Topic 11: The Periodic Table (Period 3 Elements)
X)
1. P3– Atomic and Ionic Radii depends on:
  S2–
Cl –  nuclear charge
Na  no. of quantum shell with electrons
Mg
Al   shielding effect by inner shell electrons
Si
P
radius
S Strategy:
Cl
/nm
 Ar 1) Write electronic configuration

2) Apply the above 3 factors.
(LT
Na+ 3) Conclude on nuclear attraction.
Mg2+ * If the 3 factors are the same, the reason to use
Al3+
Si4+ is due to mutual repulsion between electrons.
atomic number
Across a period, there is same number of quantum shell with electrons and the nuclear charge increases
while shielding effect by inner shell electrons is relatively constant. Hence, the nuclear attraction on the
outermost electrons increases and thus, the atomic radius decreases.
With reference to the diagram above,
 Cation has smaller radius than its corresponding atom (e.g. Mg2+ vs Mg) since the cation has one less
quantum shell of electrons after the removal of outermost electrons.
 Anion has a larger radius than its corresponding atom (e.g. S vs S2–) due to greater electron–
electron repulsion when electrons are added to the same outermost shell, resulting in the expansion
of electron cloud.
ht
 Across each isoelectronic series with same electronic configuration (e.g. from Na+ to Si4+ or from P3– to
Cl–), the radii of isoelectronic ions decreases due to an increase in nuclear charge, while shielding
effect by inner shell electrons is relatively constant and number of quantum shells with electrons is the
same.
2. Ionisation Energies (IE) depends on:

np 6  nuclear charge
[2,3,3] pattern   radius
1st IE /kJ mol–1
rig
np5
 np3  shielding effect by inner shell electrons
np4
2 np2 Strategy:
ns
1
ns np1 1) Write electronic configuration
2) Check if it is one of the 2 anomalies.
If not, apply the above 3 factors.
atomic number 3) Conclude on nuclear attraction.
 Across the period, the radius decreases and the nuclear charge increases while the shielding effect
by inner shell electrons is relatively constant. Hence, the nuclear attraction on the electron to be
removed increases and thus, 1st IE of elements generally increase.
Note: The trend (from ns1 to ns2 np6) follows a [2,3,3] pattern.
py
With reference to the above IE graph,

Mg: 1s2 2s2 2p6 3s2 Al: 1s2 2s2 2p6 3s2 3p1
The 3p electron of Al is further away from the nucleus and has a higher energy than the 3s electron of
Mg. Hence, 1st IE of Al is lower than that of Mg.
Al+: 1s2 2s2 2p6 3s2 (Mg) Si+: 1s2 2s2 2p6 3s2 3p1 (Al)
because The 3p electron of Si+ is further away from the nucleus and has a higher energy than the 3s
electron of Al+. Hence, 2nd IE of is Si lower than that of Al.
Co
P: 1s2 2s2 2p6 3s2 3p3 S: 1s2 2s2 2p6 3s2 3p4
The inter–electronic repulsion between the paired 3p electrons in S makes it easier to remove one of
the paired electrons than the unpaired 3p electrons of P which do not experience such repulsion. Hence,
1st IE of S is lower than that of P.
S+: 1s2 2s2 2p6 3s2 3p3 (P) Cl+: 1s2 2s2 2p6 3s2 3p4 (S)
The inter–electronic repulsion between the paired 3p electrons in Cl+ makes it easier to remove one
of the paired electrons than the unpaired 3p electrons of S+ which do not experience such repulsion.
Hence, 2nd IE of Cl is lower than that of S.
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 45 Topic 11: Periodic Table
(Adapted from past year JJC Inorganic Summary)
3. Structure and Bonding of Period 3 ELEMENTS
X)
Period 3 Na(s) Mg(s) Al(s) Si(s) P4(s) S8(s) Cl2(g) Ar(g)
High and  from Na to Al. Highest Low & mp of S8 > P4 > Cl2 > Ar
Giant metallic structure. Giant covalent P4, S8 and Cl2 have simple
structure. covalent structure while Ar has
A lot energy is required to simple monoatomic structure.
overcome the strong metallic A lot energy is
bonds between metal cations required to break Little energy is required to
(LT
and mobile valence electrons. the strong overcome the weak
melting/ covalent bonds instantaneous dipole-induced
boiling Increasing energy required between Si dipole (id–id) attractions between
point since the strength of metallic atoms. the molecules or between Ar
bond increases because the atoms.
charge density of metal ions
 and no. of mobile valence Since no. of electrons per
electrons  from Na to Al.) molecule of S8 > P4 > Cl2 > Ar
atom, the strength of id–id
attractions between S8 > P4 >
Cl2 > Ar atoms.
High and  from Na to Al Low Poor /non–conductor of

electrical
since no. of mobile valence (semiconductor) electricity due to the absence of
conduct–
mobile charge carriers in simple
ivity
Na to 3 in Al.
ht
electrons increase from 1 in
covalent structure.
Si
electrical conductivity
Al Al
melting point /°C
Mg Mg
rig
Na Na
S8
Si
Cl2
P4 Ar P4 S8 Cl2 Ar
atomic number atomic number
DIAGONAL Relationship
py
In the Periodic Table, certain pairs of diagonally adjacent elements in Period 2 and Period 3 (shown below)
show similarity in their properties. They are said to have a diagonal relationship.
B/Si
-
Explanation: Since electronegativity increases across the period but decreases down the group, diagonally
adjacent elements have similar electronegativity.
Co
Hence, they have similar physical and chemical properties. (e.g Li and Mg, Be and Al, B and Si)

4. Reaction of Period 3 Elements with Oxygen and Chlorine
X)
For reactions with Cl2 and O2, the ON of Period 3 elements in their chlorides and oxides is always
positive since Cl is the most electronegative element among the Period 3 elements, and O is more
electronegative than Period 3 elements.
The maximum ON of the elements increases across the period, corresponding to the number of
valence electrons used for bonding with chlorine (same as the group number).
(LT
Phosphorus can form both PCl3/PCl5 and P4O6/P4O10 because P has lowlying vacant 3d orbitals
to expand octet structure.
4.1 With Oxygen gas

[
Element Equation Remark

Vigorous, burns with a brilliant yellow
Na 4Na(s) + O2(g)  2Na2O(s)
flame.
Very vigorous, burns with a bright white
Mg 2Mg(s) + O2(g)  2MgO(s)
light.
Vigorous at first, burns with a white flame
Al 4Al(s) + 3O2(g)  2Al2O3(s) then Al2O3(s) formed on the surface prevents
ht further attack.
No reaction until 400oC and burns with white
Si Si(s) + O2(g)  SiO2(s)
flame
Limited O2: P4(s) + 3O2(g)  P4O6(s) Vigorous, burns with a bright white light or
P
Excess O2: P4(s) + 5O2(g)  P4O10(s) pale bluegreen flame.
S(s) + O2(g)  SO2(g)
rig
S Vigorous, burns with a blue flame.
Excess O2: SO2(g) + ½O2(g)  SO3(g)
Ca 2Ca(s) + O2(g)  2CaO(s) Very vigorous, burns with a brickred flame.
Very vigorous, burns with a crimsonred
Sr 2Sr(s) + O2(g)  2SrO(s)
flame.
Very vigorous, burns with an applegreen
Ba 2Ba(s) + O2(g)  2BaO(s)
flame.
py
4.2 With Chlorine gas

Period 3 Equation Remark
Na 2Na(s) + Cl2(g)  2NaCl(s) Very vigorous
Mg Mg(s) + Cl2(g)  MgCl2(s) Very vigorous
Al 2Al(s) + 3Cl2(g)  2AlCl3(s) Vigorous
Si Si(s) + 2Cl2(g)  SiCl4(l) Slow
Co
Limited Cl2: P4(s) + 6Cl2(g)  4PCl3(l)

P PCl3(l) + Cl2(g)  PCl5(s) Slow
Excess Cl2: P4(s) + 10Cl2(g)  4PCl5(s)

5.1 SUMMARY: Periodicity in the Properties of Chlorides of Period 3 Elements
Element Na Mg Al Si P
Formula NaCl(s) MgCl2 (s) AlCl3 (s) SiCl4 (l) PCl5 (s) PCl3 (l)
Oxidation No. +1 +2 +3 +4 +5 +3
T
Structure Giant Ionic Simple Covalent
Strong covalent bonds between atoms within a molecule AND
Covalent bonds, with ionic
Bonding Strong ionic bonds weak id–id attraction (except for PCl3: weak pd–pd attraction)
character,
between respective molecules.
L
Melting/
High High Low Low Low Low
Boiling point
(
Dissolves in water to give
Dissolves in water to give
[Mg(H2O)6]2+ which hydrolyses Covalent chlorides hydrolyses completely in water to give
2+ [Al(H2O)6]2+ which hydrolyses
Dissolves in water slightly in water since Mg strongly acidic solution due to formation of HCl.
slightly in water since Al3+
(hydration) to give has slightly higher charge
has high charge density and
neutral solution density than Na+ and can
can polarise O–H bond in the The central atom of the chloride has lowlying vacant 3d
t
(no hydrolysis as Na+ polarise O–H bond in the
coordinated water molecule, orbitals to form dative covalent bonds with water molecules
has low charge coordinated water molecule,
weakening the O–H bond to by accepting the lone pair of electrons on O of H2O to form an
density) weakening the O–H bond to
+ release H+ and form a weakly unstable transition state which breaks down to form HCl.
release H and form a weakly
acidic solution.
acidic solution.
h
Reaction with Eqn 1 (Hydration): Eqn 1 (Hydration): Hot excess water:
water MgCl2(s) + 6H2O(l)  AlCl3(s) + 6H2O(l)  PCl5(s) + 4H2O(l) 
Eqn (Hydration): [Mg(H2O)6]2+(aq) + 2Cl–(aq) [Al(H2O)6]3+(aq) + 3Cl–(aq) Eqn (Hydrolysis): H3PO4(aq) + 5HCl(aq)
NaCl(s)  SiCl4(l) + 2H2O(l)  Cold excess water:
Eqn 2 (Hydrolysis): Eqn 2 (Hydrolysis): SiO2(s) + 4HCl(aq)
g
Na+(aq) + Cl–(aq) PCl5(s) + H2O(l) 
[Mg(H2O)6]2+(aq)  [Al(H2O)6]3+(aq)  POCl3(aq) + 2HCl(aq)
[Mg(H2O)5OH]+(aq) + H+(aq) [Al(H2O)5OH]2+(aq) + H+(aq) OR
Approximate
pH of solution
Effect of
7
i
Extent of Hydrolysis  Charge density of Mx+
Greater extent of hydrolysis, lower the pH of the solution (given same conc)
Charge density of Na+ < Mg2+ < Al3+
r
pH of NaCl > MgCl2 > AlCl3
6.5 3
SiCl4(l) + 4H2O(l) 
SiO2 2H2O(s) + 4HCl(aq)
White fumes of HCl will be observed.

PCl3(l) + 3H2O(l) 
H3PO3(aq) + 3HCl(aq)
12
adding a
SMALL
quantity of
water py AlCl3(s) + 3H2O(l) 
Al(OH)3(s) + 3HCl(g)
white fumes
SiCl4(l) + 2H2O(l) 
SiO2(s) + 4HCl(g)
white fumes
PCl5(s) + H2O(l) 
POCl3(l) + 2HCl(g)
white fumes

5.2 SUMMARY: Reactions of Oxides/Hydroxides of Period 3 Elements with Water and with Acids/Bases
Element Na Mg Al Si P S
Formula Na2O(s) MgO(s) Al2O3(s) SiO2(s) P4O6(s) P4O10(s) SO2(g) SO3(l)
Oxidation No. +1 +2 +3 +4 +3 +5 +4 +6
T
Structure Giant Ionic Giant Covalent Simple Covalent
Strong ionic bonds Strong Si‒O Strong covalent bonds within a molecule AND
Bonding
(Al2O3: ionic bonds with covalent character) covalent bonds weak intermolecular forces of attraction between molecules
Melting/Boiling point High High High High Low Low Low
Acid/Base Nature Basic Amphoteric Acidic
L
In general, How to balance the equation?
1) determine the pdt
 metallic oxides/hydroxides  ionic  basic  react with acids
2) balance the Period 3 element
(
 nonmetallic oxides/hydroxides  covalent  acidic  react with bases
3) balance charges with H+/OH
 aluminium oxides/hydroxides  ionic with covalent character  amphoteric  react with acids and bases 4) balance eqn with H2O
Oxide Reactions WITH WATER Reactions WITH ACIDS OR BASES

Reacts vigorously with water to form a strongly alkaline NaOH(aq) solution Reacts with acid to form salt and water.
t
Na2O(s) with pH 13–14. Na2O(s) + 2H+(aq)  2Na+(aq) + H2O(l)
Na2O(s) + H2O(l)  2NaOH(aq)
Sparingly soluble in water and reacts with water to a small extent (hence Reacts with acid to form salt and water.
“” used in equation) to form limited quantity of Mg(OH)2(aq), thus a weakly MgO(s) + 2H+(aq)  Mg2+(aq) + H2O(l)
MgO(s)
h
alkaline solution with pH 9 is obtained.
MgO(s) + H2O(l)  Mg2+(aq) + 2OH(aq)
Al2O3(s) Insoluble in water due to the high magnitude of its lattice energy. Reacts with BOTH acids and alkalis to form salt and water.
Energy released on forming ion–dipole interaction is insufficient to With acid: Al2O3(s) + 6H+(aq)  2Al3+(aq) + 3H2O(l)
g
compensate the energy required to break the strong ionic bonds between With base: Al2O3(s) + 2OH–(aq) + 3H2O(l)  2[Al(OH)4]–(aq)
oppositely charged ions.
Hence, the resulting solution is neutral with pH 7.
SiO2(s)
P4O6(s)
and
P4O10(s)
Insoluble in water as
i
large amount of energy is required to break many strong Si−O covalent
bonds in the giant covalent structure of SiO2.
r
Hence, the resulting solution is neutral with pH 7.
React with water to form acidic solutions with pH 2.
P4O6(s) + 6H2O(l)  4H3PO3(aq) [phosphorous acid is a dibasic acid]
P4O10(s) + 6H2O(l)  4H3PO4(aq) [phosphoric acid is a tribasic acid]
Reacts with hot concentrated alkali to form silicate and
water. It has NO reaction with DILUTE alkali.
SiO2(s) + 2OH–(aq)  SiO32–(aq) + H2O(l)
React with alkali to form salt and water.

P4O6(s) + 8OH–(aq)  4HPO32–(aq) + 2H2O(l)
P4O10(s) + 12OH–(aq)  4PO43–(aq) + 6H2O(l)
\
SO2(g)
and
SO3(l)
y
React with water to form strongly acidic solutions.
SO2(g) + H2O(l)  H2SO3(aq) [sulfurous acid]
SO3(l) + H2O(l)  H2SO4(aq) [sulfuric acid]
p pH 2
pH 1
React with alkali to form salt and water.
SO2(g) + 2OH–(aq)  SO32–(aq) + H2O(l)
SO3(l) + 2OH–(aq)  SO42–(aq) + H2O(l)

Topic 11: The Periodic Table (Group 2 Elements)
X)
1. Group 2 elements as good REDUCING AGENTS (i.e. high tendency for M to be oxidised to M2+).
Down the group, the reducing power of Group 2 elements increases. This is supported by the
increasingly negative E (M2+/M) values.
Hence, the reactivity of Group 2 elements towards redox (i.e. reaction with water and with O2) increases.
Mg2+ + 2e–  Mg –2.38 V
Ca2+ + 2e–  Ca –2.87 V E(M2+/M) becomes more negative down the group.
(LT
Sr2+ + 2e–  Sr –2.89 V  increasing tendency for M to be oxidised to M2+.
Ba2+ + 2e–  Ba –2.90 V
Explanation: Down the group, the radius of Group 2 elements increases and hence, the sum of 1st and
2nd IE decreases and the tendency of M losing 2 electrons to form M2+ increases (i.e.
tendency of M to be oxidised to M2+ increases).
1.1 Reaction of Group 2 elements WITH WATER

Group 2 elements, except Be and Mg, reacts with COLD water to form a colourless and strongly
alkaline M(OH)2 solution and effervescence of H2(g).
M(s) + 2H2O(l)  M(OH)2(aq) + H2(g) {except for Be, Mg}
Down the group, the reactivity of Group 2 elements with H2O increases since the reducing power of M
increases.
Element Reaction with water Observations
ht
Reacts slowly with COLD water.
Mg(s) + 2H2O(l)  Mg(OH)2(aq) + H2(g)
Effervescence of H2(g) and white ppt of
Mg(OH)2 formed in a weakly alkaline
solution of Mg(OH)2(aq) of pH 9
Mg
Reacts readily with STEAM to form
MgO(s) and H2(g). Mg glows in steam to give a white residue
of MgO(s) & effervescence of H2(g).
Mg(s) + H2O(g)  MgO(s) + H2(g)
Effervescence of H2(g) and a strongly
Reacts readily with COLD water to form
alkaline solution of pH 12 formed.
rig
Ca Ca(OH)2(aq) and H2(g).
White Ca(OH)2 ppt. may appear due to low
Ca(s) + 2H2O(l)  Ca(OH)2(aq) + H2(g)
solubility of Ca(OH)2.
Reacts vigorously with COLD water to
Sr form M(OH)2(aq) and H2(g). Effervescence of H2(g) and a strongly
M(s) + 2H2O(l)  M(OH)2(aq) + H2(g) alkaline solution of pH 12–14 formed.
Ba {where M = Sr, Ba}
Note: Solubility of the resulting M(OH)2 in water increases down the group:
 Mg(OH)2: appears as a white ppt.,
 Ba(OH)2: appears as a colourless solution.
Due to the increasing solubility of M(OH)2, the pH of the resulting hydroxide solutions increases.
py
(i.e. from pH 9 in Mg(OH)2 to pH 12 in Ca(OH)2 to pH 14 in Ba(OH)2).
1.2 Reaction of Group 2 elements WITH OXYGEN

Group 2 elements, except Be, burn in O2 to form a white simple metal oxide, MO.
M(s) + ½O2(g)  MO(s) {except for Be}
Down the group, the reactivity of Group 2 elements with O 2 increases since the reducing power of M
increases.
The resulting Group 2 oxides, except BeO, are ionic and basic and react with water to form
hydroxides.
Co
Note: BeO is covalent with ionic character  amphoteric oxide (diagonal relationship with Al2O3)
Element Equation Remark

Mg Mg(s) + ½ O2(g)  MgO(s) Very vigorous, burns with a brilliant white flame.
Ca Ca(s) + ½ O2(g)  CaO(s) Very vigorous, burns with a brick red flame.
Sr Sr(s) + ½ O2(g)  SrO(s) Very vigorous, burns with a crimson red flame.
Ba Ba(s) + ½ O2(g)  BaO(s) Very vigorous, burns with an apple green flame.
2. THERMAL STABILITY of SOLID Nitrates, Carbonates and Hydroxides of Group 2 elements
M(NO3)2(s)  MO(s) + 2NO2(g) + ½ O2(g) Thermal stability of Group 2 compounds depends on
X)
MCO3(s)  MO(s) + CO2(g)  Polarising power of M2+ cation
M(OH)2(s)  MO(s) + H2O(g) Higher the charge density of M2+, stronger the polarising
power of M2+.
 Polarisability of the Anion
Larger the size of anion, greater its polarisability.
2.1 Group Trend (using MCO3 as example)

Since the ionic radius of M2+ increases down the group, the charge density of M2+ decreases.
(LT
Hence, the ability of M2+ to polarise the large anion decreases and the CO bond in CO32 is
weakened to a smaller extent.
Thus, the thermal stability of MCO3 increases (or decomposition temperature increases or ease of
decomposition decreases) down the group.
2.2 Making Comparison (using Mg(NO3)2 and Ba(NO3)2 as examples)

Since Mg2+ has smaller radius, Mg2+ has higher charge density than Ba2+. Hence, Mg2+ polarises
the large NO3– more and weaken the N –O bond in NO3 more than Ba2+.
Thus, Mg(NO3)2 is thermally less stable and decomposes at a lower temperature than Ba(NO3)2.
3. Other Information on Group 2 elements and compounds
3.1 Enthalpy change of hydration (Hhyd)

ht
Since the radius of M2+ increases down the group, the charge density of M2+ decreases and hence,
the strength of ion–dipole interaction formed between M2+ and H2O molecules decreases (i.e. less
heat is released).
Thus, Hhyd becomes less exothermic down the group.
3.2 Solubility of MSO4 (Hsoln = LE + Hhyd)

rig
Solubility of MSO4 decreases down the group because the decrease in |LE| is more than the
decrease in |Hhyd| (i.e. energy released is insufficent to compensate the energy required).
 MgSO4 and CaSO4 dissolve in water to give a colourless solution;
 SrSO4 and BaSO4 are white ppt. insoluble in water.
py
Co

Topic 11: The Periodic Table (Group 17 Elements)
X)
1. Group 17 elements as OXIDISING AGENTS (i.e. high tendency for X2 to be reduced to X)
Down the group, the oxidising power of Group 17 elements X2 decreases. This is supported by the
decreasingly positive E (X2/X–) values.
Hence, the reactivity of Group 17 elements towards redox decreases.
Cl2 + 2e–  2Cl– +1.36 V E(X2/X–) becomes less positive down the group.
Br2 + 2e–  2Br– +1.07 V  decreasing tendency for X2 to be reduced to X–.
I2 + 2e–  2I– +0.54 V
(LT
Explanation: Down the group, the electronegativity of X decreases and hence, the tendency of X gaining
an electron to form X decreases (i.e. tendency for X2 to be reduced to X– decreases).
REDOX Reactions illustrating the Trend in Oxidising Power of X2

Reactions Evidence
 Cl2, a stronger oxidising agent than Br2 and I2, can oxidise Br– to Br2 and I to I2.
Cl2 + 2Br–  Br2 + 2Cl– Ecell = (+1.36) – (+1.07) = +0.29 V > 0
Cl2 + 2I  I2 + 2Cl
– –
Ecell = (+1.36) – (+0.54) = +0.82 V > 0
Displacement
 Br2, a stronger oxidising agent than I2 only, oxidises I– to I2 but not Cl2 to Cl–.
Br2 + 2I–  I2 + 2Br– Ecell = (+1.07) – (+0.54) = +0.53 V > 0
Br2 +2Cl  no reaction Ecell = (+1.07) – (+1.36) = –0.29V < 0
–
 Ecell for Cl2 = (+1.36) – (+0.77) = +0.59 V > 0

ht
Equation: Cl2 + 2Fe2+  2Cl–+ 2Fe3+
 Ecell for Br2 = (+1.07) – (+0.77) = +0.30 V > 0
Equation: Br2 + 2Fe2+  2Br– + 2Fe3+
Reactions of
X2 with Fe2+  Ecell for I2 = (+0.54) – (+0.77) = 0.23 V < 0 (not energetically feasible)
Equation: Br2 + 2Fe2+  2Br– + 2Fe3+
rig
Cl2 and Br2, being stronger oxidising agents than I2, oxidise Fe2+ to Fe3+ while I2 (the
weakest oxidising agent) cannot.
 Cl2 and Br2, being stronger oxidising agent, oxidise S2O32– to SO42–.
Oxidation number of S increases by 4 units from +2 in S2O32– to +6 in SO42–.
Reaction of
4X2 + S2O32– + 5H2O  8X– + 2SO42– + 10H+ (where X = Cl and Br)
X2 with S2O32–
(thiosulfate  I2, being a weaker oxidising agent, oxidises S2O32– to S4O62–.
ion) Oxidation of S increases by 0.5 units from +2 in S2O32– to +2.5 in S4O62–.
I2 + 2S2O32–  2I– + S4O62–
py
2. THERMAL STABILITY of GASEOUS Group 17 Hydrides (HX)

Thermal stability of HX depends on strength of H– X bond.
2HX(g)  H2(g) + X2(g)
Since the atomic radius of X increases from Cl to I, H–X bond becomes longer, weaker and hence, the
ease of breaking H–X bond increases from HCl to H–I.
Hence, the thermal stability of HX decreases down the group.
Co
HX Observations
HCl Does not decompose even when heated strongly
HBr Redbrown fumes of Br2 when heated strongly
HI Violet fumes of I2 obtained when a redhot rod is plunged into a gas jar of HI
Note: Down the group, the  in E(H–X) is more significant than the  in E(X–X) and hence, Hdecomposition of
HX becomes increasingly exothermic (i.e. increasing reactivity)!
Hdecomp = 2E(H–X) – E(H–H) – E(X–X)

3. Other Information on Group 17 elements and compounds
3.1 Volatility of Group 17 elements
X)
Increasing amount of energy is required to overcome the increasing strength of instantaneous
dipole–induced dipole attraction between respective X2 molecules since the number of electrons
per X2 molecule increases down the group.
Hence, the boiling point of X2 increases and the volatility of halogens (X2) decreases.
3.2 Reaction of X2 with H2

X2(g) + H2(g)  2HX(g) Hr = [E(XX) + E(HH)] – 2E(HX)
The decrease in E(H–X) is more significant than E(X–X), causing H to become less exothermic.
(LT
extent of reaction Hr / kJ mol–1
explode with H2(g) in bright sunlight but reacts
Cl2 –182
slowly in the dark; reaction is complete.
react with H2(g) only upon heating to 200 °C over Pt
Br2 –103
catalyst.
react at 400°C over Pt catalyst to form an
I2 –11
equilibrium mixture, reaction is slow and reversible.
3.3 Acid Strength of HX(aq)

H–X(g)  H+(aq) + X–(aq)
Since H–X is more readily ionised from HCl to HBr to HI, the acid strength of HX(aq) increases.
Note: All HX(aq) ionises completely in dilute aqueous solution to give H+(aq) and X–(aq) (i.e. strong
ht
acid) except HF(aq) which is a weak acid.
3.4 Reactions of halide ions, X–(aq) with Ag+(aq), followed by NH3(aq)

All AgX are insoluble/sparingly soluble in water.
Halide X– Observation upon addition of Ag+(aq), followed by NH3(aq)
White AgCl ppt is soluble in both dilute and conc. NH3(aq) to form a colourless Ag(NH3)2+
Cl–(aq)
complex and Cl–(aq).
rig
Cream AgBr ppt is sparingly soluble in dilute NH3(a) but soluble in conc. NH3(aq) to
Br–(aq)
form a colourless Ag(NH3)2+ complex and Br–(aq).
I–(aq) Yellow AgI ppt is insoluble in both dilute and conc. NH3(aq).
Explanation: Ag+(aq) + 2NH3(aq)  Ag(NH3)2+(aq)

When NH3(aq) is added, Ag+(aq) forms a stable Ag(NH3)2+ complex, reducing [Ag+] such that ionic product
< Ksp at that instant. This causes the position of equilibrium of AgX(s)  Ag+(aq) + X–(aq) shifts right to
produce some Ag+.
The solubility of ALL AgX(s) in NH3(aq) is higher than that in water.
py
Since Ksp of AgCl > Ksp of AgBr > Ksp of AgI, solubility of AgX in NH3(aq) decreases down the group.
Hence, AgCl completely dissolves in NH3(aq) whereas AgBr partially dissolves in NH3(aq) and AgI still remain
essentially insoluble in NH3(aq).
3.5 Unique QA reaction of I with Cu2+
Halide X–(aq) Cl–(aq) Br–(aq) I–(aq)

White CuI ppt in brown I2 solution formed.
Cu2+ + I  2CuI + I2
Co
Add Cu2+(aq),
followed by No ppt formed. No ppt formed. Brown I2(aq) reduced to colourless I–(aq)
S2O32–(aq) by S2O32–(aq).
dropwise No colour change No colour change I2 + 2S2O32–  2I– + S4O62–
until in of solution. of solution.
excess White ppt soluble in excess S2O32–(aq) to
form a colourless Cu(S2O3)– complex.
CuI + S2O32–  Cu(S2O3)– + I–

Topic 21: Introduction to the Chemistry of Transition Elements
X)
1 Definition: A transition element (TE) is a d–block element that forms one or more stable ions
with partially filled d–orbitals (i.e. its configuration cannot be d 0 or d10).
2 Physical Properties of TE and Contrast Physical Properties of TE with Ca (main Group elements)
Physical
Trend across first row TE Compared to Ca (s–block metal)
(LT
Property
Relatively constant since the Smaller than Ca since TE has a
1) same no. of quantum shells with 1) greater nuclear charge and
electrons; 2) poor shielding effect by inner 3d
atomic and ionic 2)  in nuclear charge electrons.
radii 3)  in shielding effect by more inner Note:
shell 3d electrons In TE, electrons are added to the d–orbitals
which are diffused and provide poor
shielding of 4s electrons from the nucleus.
Relatively constant since the Higher than Ca since TE has a

1) radii of TE are relatively constant and 1) greater nuclear charge and
1st IE
2)  in nuclear charge 2) smaller radius while
(removes electron
3)  in shielding effect by more inner 3) poor shielding effect by inner 3d
from 4s orbital)
ht
shell 3d electrons electrons.
Higher than Ca since

More energy is required to overcome the
stronger metallic bonds in TE due to
high melting point 1) higher charge density of TE cations

(higher charge and smaller radius)
rig
melting point due to strong metallic bond
2) more mobile valence electrons (both
3d and 4s) available for metallic
bonding due to the small energy
difference of 3d and 4s orbitals.
Higher than Ca since TE has

good electrical conductor 1) more mobile valence electrons (both
electrical due to the presence of 3d and 4s) available as charge carrier
conductivity mobile valence electrons due to the small energy difference of
as mobile charge carrier. 3d and 4s orbitals.
py
density High and increase gradually from Cr to Higher than Ca since TE has
(depends on a Cu since there is 1) higher atomic mass,
combination of 1) an increase in relative atomic mass
factors: atomic
2) smaller atomic radii and
mass, atomic radius 2) while radii remains relatively constant. 3) close–packed structure.
and arrangement of
particle in the crystal
lattice)
Co
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 54 Topic 21: Transition Elements

3 Characteristics Properties of TEs and their Compounds
3.1 TEs exhibit variable oxidation states in their compounds because variable number of
X)
electrons from 3d and 4s orbitals can be involved in bonding as 3d and 4s orbitals
have similar energies.
 Lowest oxidation state involves the loss of electrons from 4s orbital (i.e. ionic bonding involved).
Highest oxidation state involves all electrons in the partially–filled 3d orbitals (i.e. the unpaired 3d
electrons) and all electrons in 4s orbital (i.e. covalent bonding involved).
e.g. Co: [Ar] 3d7 4s2  highest O.S. of Co = +5
(LT
 Main group metals exhibit fixed oxidation states (e.g. +2 in Ca compounds) because they can only lose
a fixed number of electrons from their outermost shell since the removal of next electron from an inner
shell requires a much higher IE.
3.2 TEs have strong tendency to form complexes via dative bond formation since
transition metal cations have
 high charge density to attract lone pair from the ligand and
 low–lying vacant orbitals to accept lone pair from the ligand
Note:Some main group elements (e.g. Al and Pb) can also form complexes (e.g. [Al(OH)4]–, [PbCl4]2–).
ht
 Definition of Complex : Complex ion consists of a central metal atom/ion surrounded by ligands via dative
bond formation.
 Definition of Ligand : Ligand is an anion or neutral molecule that has at least one lone pair of electrons to
form dative bond with the central metal atom/ion.
rig
 Net charge of complex = (O.S of :L) + (O.S of metal ion)

Example: Calculate the oxidation number of M in [M(SCN)(H2O)5]Cl2
py
1 0 1
Let the oxidation number of M be x.
(x) + (1) + 5(0) + 2(1) = 0 OR (x) + (1) + 5(0) = 2
 x = +3  x = +3
Note:In this case, Cl is a counter–anion that forms ionic bond with the
complex cation [M(SCN)(H2O)5]2+, not a ligand (that form dative
bond with central metal atom/ion)
 Coordination number = no. of dative bonds formed around the central metal atom/ion
Co
In general, TE complexes have a coordination number of 6 except for Ag (coordination no. of 2)

Exception: Complexes with halides (e.g CuCl42–, FeCl4–) and complexes involving transition elements ions
with d10 configuration (e.g Ag(NH3)2+, CuCl2–).
Recall: Main group and Zn complexes have a coordination number of 4 (eg. Al(OH)4–, Zn(NH3)42+).

 In aqueous state, TE ions exist as [M(H2O)6]n+ hydrated complex.
For ions with high charge density (e.g Fe3+ and Cr3+), the hydrated complex hydrolyses to form weakly
X)
acidic solution. The high charge density MX+ polarise and weaken the O–H of the coordinated H2O to
produce H+.
[M(H2O)6 ]3+(aq)  [M(H2O)5OH]2+(aq) + H+(aq), where M: Al, Fe, Cr
 Hypothetical cations like Cr6+(aq) and Mn7+(aq) does not exist. Instead, they exist as covalently
bonded oxo–compounds such as CrO42 and MnO4.
These hypothetical cations have very high charge density (high charge, small radius) and hence they
have very high polarising power to distort the electron cloud of H2O molecule to a very large extent such
that the bonding becomes covalent. Also, very high ionisation energies are required to form these
(LT
cations (i.e. not energetically favourable).
Formation of Complex ion by Ligand Exchange
Colour change of TE complexes

(because of a change in the size of d–orbital splitting, E)
due to due to
Ligand exchange Redox reactions
(change in O.S of
central metal ion)
A complex ion can undergo ligand exchange when:
3.2.1 Ligand strength(stronger ligand displaces weaker ligand to form more stable complex)
Example 3.2.1(a)
Observation
ht Explanation
When aq KSCN [Fe(H2O)6] (aq) + SCN–-(aq)  [Fe(SCN)(H2O)5]2+(aq) + H2O(l)
3+
is added to aq pale yellow blood–red

FeCl3, a blood– 
Stronger SCN ligand displaces the weaker H2O ligand to form a stronger
red solution is
dative bond with Fe3+ to give a more stable [Fe(H2O)5(SCN)]2+(aq) complex.
formed.
rig
When aq NaCN [Fe(SCN)(H2O)5]2+(aq) + 6CN–-(aq)  [Fe(CN)6]3–(aq) + SCN–-(aq) + 5H2O(l)
is added to the orange–brown
resulting Stronger CN ligand displaces the weaker SCN ligand to form a stronger
mixture, orange dative bond with Fe3+ to give a more stable [Fe(CN)6]3(aq) complex.
brown solution
Strength of ligand: H2O < SCN– < CN–
is formed.
Example 3.2.1(b)
Observation Explanation
When dilute aq. NH3(aq) + H2O(l)  NH4+(aq) + OH(aq)
py
NH3 is added to Aqueous NH3, which is a weak base, ionises partially in H2O to give OH that
aq. CuSO4, a reacts with Cu2+(aq) to give blue Cu(OH)2 ppt.
pale blue ppt is
formed. Cu2+(aq) + 2OH(aq)  Cu(OH)2(s)
blue soln pale blue ppt
The pale blue [Cu(H2O)6]2+(aq) + 4NH3(aq)  [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
ppt dissolves in dark blue soln
excess NH3(aq) Stronger NH3 ligand displaces the weaker H2O ligand from [Cu(H2O)6]2+(aq)
to form a dark by forming a stronger dative bond with Cu 2+ to give a more stable
blue solution. [Cu(NH3)4(H2O)2]2+ complex.
Co
Cu(OH)2(s)  Cu2+(aq) + 2OH(aq) ---(1)

Formation of [Cu(NH3)4(H2O)2]2+ decrease the concentration of [Cu(H2O)6]2+
and causes the position of equilibrium 1 to shift right so as to form back
some Cu2+.
Cu(OH)2 ppt dissolves in excess NH3(aq) to give a dark blue solution.
Note: Cu(OH)2 is a sparingly soluble salt and Cu2+ exists as [Cu(H2O)6]2+ in aqueous
solution.

Example 3.2.1(c) (Application)
Hb + 4O2  Hb(O2)4
X)
Hb + 4CO  Hb(CO)4
In haemoglobin, the O2 molecule is bonded reversibly to the Fe2+ ion by dative bond, thus allowing
haemoglobin to carry oxygen from one part of the body to another.
The stronger CO (or CN–) ligand displaces the weaker O2 ligand to form a stronger dative bond with
Fe2+ to give a more stable complex.
 This results in the inability of haemoglobin to transport oxygen to the cells and thus accounts for the
toxic nature of CO.
*Note: CO poisoning can be treated when the affected patients are subject to high [O2] (i.e. Le Chatelier’s
(LT
Principle).
3.2.2 Ligand Concentration (Le Chatelier’s Principle)

Observation Explanation
When conc. HCl is [Cu(H2O)6] (aq) + 4Cl (aq)  [CuCl4]2(aq) + 6H2O(l) ---(2)
2+ 
added aq. CuSO4, yellow soln

a yellow solution is
formed. When concentrated HCl is added, the high [Cl] causes the position of
equilibrium 2 to shift right, forming yellow [CuCl4]2(aq).
Note: When only a few drops of concentrated HCl is added, the colour of the solution
appears green due to the mixing of blue [Cu(H2O)6]2+ (originally present) with the
yellow [CuCl4]2 formed. The yellow solution is only observed when an excess
of concentrated HCl is added.
When water is then When excess water is added, the concentrations of all aqueous species
are reduced. This causes the position of equilibrium 2 to shift left since
added in excess, a
pale blue solution
is formed
ht
there are more concentration terms on the left hand side
The colour of the solution becomes pale blue.
3.3 TE complexes and compounds are usually coloured due to dd transition.
In a complex ion, the presence of ligands causes the d orbitals to split into 2 different
rig
energy levels with relatively small energy difference.
Radiation from the visible light region of the electromagnetic spectrum is absorbed
when an electron transits from a d orbital of lower energy to another unfilled/partially
filled d orbital of higher energy.
Hence, TE complexes are coloured and the colour observed is the complement of the
colours absorbed.
py
For an octahedral complex, the splitting of d subshells occurs when the electrons in dz2 and dx2-y2 orbitals
point towards the lone pair of the incoming ligands, resulting in repulsion between the electrons.
This causes the  in energy to be greater for dz2 and dx2-y2 orbitals.
Co
Figure 1: Splitting of the 3d–orbitals of Ti3+ in an octahedral complex such as [Ti(H2O)6]3+.

In order for electron transition to occur between the 2 sets of d orbitals, the metal ion must have the following:
 at least one d electron (to make the transition), and (d0 cannot!)
X)
 partially–filled or empty d orbital in the higher energy level. (d10 cannot!)
Cu(I) compound, such as Cu(S2O3) is colourless, is usually not coloured as d–d transition is not
possible.
(LT
hc
Since E = ( is the wavelength of radiation absorbed), if the energy gap (E) is

 small, radiation of longer wavelength (i.e. orange or red) is absorbed  colour seen is cyan or blue.
 large, radiation of shorter wavelength (i.e. blue or cyan) is absorbed colour seen is orange or red.
Factors affecting d orbital splitting (E):

 (Given same central metal ion) Change in ligands result in different d orbital splitting
Ligand exchange results in colour change. (See Section 3.2.1).
 (Given same ligands) Change in O.S of central metal ions results in different d–orbital splitting
Redox reaction results in colour change.
3.4.1
ht
Transition elements and their compounds can function as homogeneous catalysts
because of their ability to vary their oxidation state since the 3d and 4s orbitals have
similar energies.
Homogeneous catalysts: Catalysts and reactants are in the same physical phases.
Example:
rig
S2O82(aq) + 2I(aq)  2SO42(aq) + I2(aq) Ecell = +1.47 V
Since Ecell is greater than zero, this implies that the reaction is energetically feasible.
However, the reaction is slow to proceed due to the high activation energy of the reaction since
the two negatively charged ions, S2O82(aq) and I(aq), would repel each other.
A catalyst is used to speed up the slow reaction and the catalyst chosen must be:
 kinetically favoured (oppositely charged)
 thermodynamically favoured (Ecell > 0)
If Fe2+(aq) is added as catalyst, the reaction occurs via an alternate pathway via two steps:
py
Species present: I, S2O82 and Fe2+

S2O8 2– + 2e-  2SO4 2– E = +2.01 V --  [R]
I2 + 2e-  2I– E = +0.54 V --  (more –ve but not kinetically favoured)
Fe3+ + e-  Fe2+ E = +0.77 V --  [O]
+: Ecell = (+2.01) – (+0.77) = +1.24 V > 0 (energetically feasible)
Step 1: S2O82(aq) + 2Fe2+(aq)  2SO42(aq) + 2Fe3+(aq)
Co
Species present: I and Fe3+(formed in step 1)

I2 + 2e-  2I– E = +0.54 V --  [O]
Fe3+ + e-  Fe2+ E = +0.77 V --  [R]
+: Ecell = (+0.77) – (+0.54) = +0.23 V > 0 (energetically feasible)
Step (2): 2Fe3+(aq) + 2I(aq)  2Fe2+(aq) + I2(aq)
Overall: S2O82(aq) + 2I(aq)  2SO42(aq) + I2(aq)

Note: Other TE ions can be possible homogeneous catalyst for the above reaction if they fulfill the following:
 Both oxidised and reduced species of TM ion must be a cation to attract S2O82 and I anions.
X)
 +0.54 V < E(Mx+/My+) < +2.01 V (so that Ecell > 0)
Example:
Since +0.54 V < E(Co3+/Co2+) < +2.01 V, Co3+ and Co2+ are possible homogeneous catalysts.
Although +0.54 V < E(Cr2O72–/Cr3+) = +1.33 V < +2.01 V, Cr2O72– & Cr3+ are not possible homogeneous
catalysts since Cr2O72– is negatively charged.
(LT
3.4.2 Transition elements and their compounds can function as heterogeneous catalysts
because of the availability of their partially–filled 3d orbitals which allow adsorption of
reactants molecules on catalyst surface.
Heterogeneous catalysts: Catalysts and reactants are in the different physical phases.
 Adsorption of reactant molecules on the solid catalyst surface occurs via the formation of dative
covalent bonds between reactant molecules and the surface catalyst atoms.
 This adsorption weakens and breaks the bonds of the reactants in the reactant molecules. and increase
surface concentration of reactants
 A different reaction mechanism with lower Ea than the uncatalysed reaction takes place.
Examples of industrial heterogeneous catalysts:
 Fe(s) in the Haber Process

ht
 Ni(s) in the hydrogenation of alkenes (manufacture of margarine)
: N2(g) + 3H2(g)  2NH3(g)
 V2O5(s) in the Contact Process : 2SO2(g) + O2(g)  2SO3(g)
Things to note:
 Catalyst speeds up the forward and the reverse reactions by the same extent. Hence, a catalysed reaction
does not yield more product than an uncatalysed reaction, but it yields the product more quickly.
rig
 Catalyst does not alter the enthalpy change of reaction.
Some Common Complexes and their Colours
Cr3+ Fe2+ Fe3+ Cu2+ Others

H2O [Cr(H2O)6]3+ [Fe(H2O)6]2+ [Fe(H2O)6]3+ [Cu(H2O)6]3+
green pale green pale yellow blue
OH Cr(OH)3(s) Fe(OH)2(s) Fe(OH)3(s) Cu(OH)2(s) [Al(OH)4],
py
grey–green ppt green ppt red–brown ppt blue ppt [Zn(OH)4]

[Cr(OH)6]3(aq) colourless
dark green
NH3 [Cu(NH3)4(H2O)2]2+ [Zn(NH3)4]2+
dark blue [Ag(NH3)2]+
colourless
Cl [CuCl4]2 yellow
[CuCl2]  colourless
CN [Fe(CN)6]4 [Fe(CN)6]3
yellow orange brown
Co
SCN [Fe(H2O)5SCN]2+
bloodred


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Jurong Pioneer Junior College

PHYSICAL & INORGANIC CHEMISTRY SUMMARY

Section B: Inorganic Chemistry Summary

2 Behaviour of Particles under the effect of Electric field...

 Direction: opposite attracts

nucleus ATOM principal quantum shells (pqs)

protons and neutrons subshells orbitals contains

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 1 Topic 1: Atomic Structure

 Hund’s Rule : When electrons are added successively to a set of degenerate

 Configuration of Ions: Always write the electronic configuration of atom first!

 Position in Periodic Table: Use this to derive electronic configuration quickly.

Exceptions: Cr is [Ar] 3d5 4s1, not 3d4 4s2!

With reference to the diagram above,

 nth IE of consecutive elements

With reference to the above IE graph,

has a higher energy than the 3s electron of Al+.

 Successive IEs of an element

Hence, the element has 2 valence

Feature : (No. of sharp increase in IE)

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 4 Topic 1: Atomic Structure

Recognise that bonding is a continuum in terms of EN difference

Ionic Bonding Covalent Bonding Metallic Bonding

(with no net dpm) (with net dpm)

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 5 Topic 2: Chemical Bonding

2 electron pairs 3 electron pairs 4 electron pairs

For trigonal bipyramidal,

For octahedral, the lone

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 6 Topic 2: Chemical Bonding

After determining the shape of the molecules,

Also has HB if there is

3 Types of Covalent Bonds...

Hydrogen bonds can be used to explain the

but is not very soluble in water, it is due to

Bulky, non–polar phenyl group hinders the

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 7 Topic 2: Chemical Bonding

2019 JPJC J2 H2 Chemistry (9729) / LeeTX

Topic 2: Chemical Bonding

 Explaining electrical conductivity...

Both Mg and Na have giant metallic structure.

Both MgF2 and NaF have giant ionic structure.

Marking Points/Strategy: (for detailed explanation ) Example:

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 9 Topic 2: Chemical Bonding

2 Definition of Ideal Gas....

Note: 1 bar = 105 Pa, 1 atm = 101325 Pa

Other formula related to gas:

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 10 Topic 3: The Gaseous State

4 Deviation from Ideal Gas Behaviour...

 Effect of Temperature (under constant p):

 Nature of gas (for comparison between two different gases):

the volume of gas particles is significant compared to that of gas.

2019 JPJC J2 H2 Chemistry (9729) / LeeTX 11 Topic 3: The Gaseous State

× vol. of solution  vol. of solution

4 Calculation using Combustion data (volume of gases)...

volume ratio 10 cm3

)cm3 10x cm3 –

Compared to gases, volume of liquids are negligible.

Before After reaction & After reaction

5 General strategy to solve stoichiometry questions...

Other useful formula:

mass of pure compound

[X] in VA cm3 of solution = [X] in VB cm3 of solution Example

8 Double Indicator Titrations...

Reaction 2 : HCO3–(aq) + H+(aq)  CO2(g) + H2O(l) (end–point determined by methyl orange)