1819 Physical and Inorganic Summary PDF
1819 Physical and Inorganic Summary PDF
1819 Physical and Inorganic Summary PDF
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2019 JC2 H2 Chemistry (9729)
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Section A: Physical Chemistry Summary
Topic
1 Atomic Structure
Content Page
KEEP CALM
14
2 Chemical Bonding 59 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
ht 32 35
9 Electrolytic Cells 36 38
16 Acids, Bases & Solubility Equilibria 39 44
* 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
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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 ). –
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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.
3 Electronic Configuration...
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
Electronsinbox notation
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s orbital (spherical) p orbital (dumb–bell shaped)
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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.
ht
(Note: Fill 4s then 3d orbitals!)
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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
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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.
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–
py
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.
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 3 Topic 1: Atomic Structure
(Adapted from past year JJC Physical Summary)
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.
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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.
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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
P: 1s2 2s2 2p6 3s2 3p3 S: 1s2 2s2 2p6 3s2 3p4
st
1 IE of S is lower than that of P because of the interelectronic 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
ht
electrons of S+ which do not experience such repulsion.
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.
py
the total number of quantum shell (i.e. Period number) is the number of sharp increase + 1.
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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
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Metallic
IMF : between + end of a molecule and of another molecule
Between Between
Nonpolar molecules Polar molecule
py
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 electrondeficient
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)
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(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
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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’
6 electron pairs
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
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Note: polar bonds polar molecule
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& linear
Note: In all covalent bonds, bond is always formed first. one bond
ht
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 HN/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.
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
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 (CC vs C=C vs CC) 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 (CC vs C=C vs CC)
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
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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)
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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 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
py
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.
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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.
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Note: If you are asked to quote the assumptions, quote in the above order of importance!
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
Extension of formula:
Molar Mass, Mr Density, (in g m3) Concentration, c (in mol m3)
m m m n
Since =
rig
Since n = , pV = RT , Since c = ,
Mr Mr V V
p Mr p
Mr =
mRT density, (in g m3) = c (in mol m3) =
pV RT RT
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.
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).
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Let y = p and x = V,
nRT k
pV = nRT p = (i.e. plot a graph of y = )
V x
V
real gas
n ideal gas
deviation from ideal
gas behaviour
rig
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.
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.
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.
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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
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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
6.021023 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 6.021023 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 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
Co
× 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 mol1.
[[
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 12 Topic 4: Atoms, Molecules & Stoichiometry
(Adapted from past year JJC Physical Summary)
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
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!
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 13 Topic 4: Atoms, Molecules & Stoichiometry
(Adapted from past year JJC Physical Summary)
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)
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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
rig
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.
pH
Case 1: Only CO32– present in original sample
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 14 Topic 4: Atoms, Molecules & Stoichiometry
(Adapted from past year JJC Physical Summary)
Case 3: CO32– & HCO3 present in original sample pH
X)
Since 1CO32(original) 1HCO3(produced),
volume of HA for reaction 1 = x cm3 810 × reaction 1 completed
volume of HA for reaction 2 = x cm3
volume of HA for complete reaction of CO32
= 2x cm3
35 × 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
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)
rig
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 15 Topic 4: Atoms, Molecules & Stoichiometry
(Adapted from past year JJC Physical Summary)
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.
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c) Balance Hydrogen using H+.
d) Balance overall charge using electrons.
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?
rig
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.
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 16 Topic 4: Atoms, Molecules & Stoichiometry
(Adapted from past year JJC Physical Summary)
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
reactant product
ΔH < 0
ΔH > 0
product reactant
2 Definitions....
rig
Hr 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
Hf 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) Hf of NaBrO3(s)
py
2
Hf can be endothermic or exothermic. However, Hf(elements in its standard state) is zero.
Hc 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) Hc of CH3CH2OH(l)
Mg(s) + ½O2(g) MgO(s) Hc of Mg(s)
Hc is always exothermic.
Co
Hneut 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) Hneut
H+(aq) + OH(aq) H2O(l) Hneut
Hneut is always exothermic and has a value of 57 kJ mol1 for strong acid–strong base reaction.
X)
Enthalpies that form gaseous atoms:
Hat 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) Hat of Br(g)
Hat is always endothermic.
E(AB) 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.
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.
Hhyd 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) Hhyd of Mg2+(g)
charge of ion
Hhyd is always exothermic and |Hhyd| which is also a measure of the strength of
size of ion
py
Hsoln 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) Hsoln of MgBr2(s)
Hsoln can be endothermic or exothermic.
Marking points for comparing LE: Marking points for comparing Hhyd:
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heat change of reaction (q) = msolcsolT + CcalT
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,
(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 Tf
corrected T f
ht Ti
the ionic compound due to polarisation (high charge density of cation and large size of anion).
q = mcT (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.
By Hess’ Law, H = H1 + H2 By Hess’ Law, H1 = (H3 + H4) H5
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 = aiHf(products) aiHf(reactants)
(b) All data given are Hc: (b) All data given are Hc:
H = aiHc(reactants) aiHc(products)
ht
(c) All data given are BE: (c) All data given are BE:
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H = E(reactants) E(products)
(d) Born–Haber cycle: (for ionic compounds) (d) Born–Haber cycle: (for ionic compounds)
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
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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.
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.
X)
(LT
G = H TS Forward reaction is Forward reaction is
energetically feasible NOT energetically feasible
Units of G is kJ mol1 (Rf > Rb) (Rf < Rb)
H is kJ mol1
S is J mol1 K1 G < 0 G = 0 G > 0
T is in K Reaction is at equilibrium
(Rf = Rb)
Example: phase change
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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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
0 t/s t/s
t1
Fig 1.1
ht
Concentration of reactant A or B vs time
0
Fig 1.2 Concentration of product C vs time
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.
py
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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T
w.r.t. [A] (or pA) rate is independent of [A] Rate [A] Rate [A]2
dA dA
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
L
[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
= dA 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
rateconc. 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
yaxis = rate
xaxis = [A]
(0,0)
(or [A]n)
*must start from
Graph to plot in
k’
r ig
1. [A] against time
0
[A] /mol dm –3 0
k’ = |grad|
2
[A] /mol dm
y
0
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
ht
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,
rig
[intermediate] should be expressed in terms of [reactant].
Ea,1
py
Ea,2
intermediate
reactant
Hr
product
progress of reaction
forward backward
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X)
Higher the frequency of effective collisions between particles, faster the rate of reaction.
(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
rate of reaction is higher
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).
0
Ea,cat Ea energy
Note: Since there is no change in temperature, Boltzmann distribution graph will not shift.
X)
(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]
ht
linear 1st order wrt [substrate]
0 [substrate]
rig
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).
1
(if fixed change is amt of product formed), rate
time
e.g. Yellow ppt. of sulfur is formed when S2O32– is reacted with H+.
Co
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.
X)
Examples of physical quantity: volume of gas, mass of reaction mixture, colour intensity, volume of titrant
gas syringe
(LT
small test
tube
electronic
balance
ht
50.51
HCl(aq)
0 t time /s
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.
(LT
(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
rig
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.
(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
Co
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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.
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
py
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
Co
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.
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
(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
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
ht
salt bridge
anode anode cathode
electrolyte
rig
2 Definition 1: Standard electrode potential of a half–cell, E, is the relative potential of this
py
Definition 2: Standard hydrogen electrode consists of H2 gas at 1 bar bubbling over platinised Pt
electrode which is dipped into 1 mol dm3 H+ solution at 298 K.
2H+(aq) + 2e H2(g) E(H+/H2) = 0.00 V
Definition 3: Standard cell potential, Ecell, is the electromotive force (e.m.f.) of a galvanic cell which
Co
X)
(LT
If one of the half–cell is S.H.E:
ht
Ecell = Ered Eox = 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
rig
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).
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
X)
(a) the voltage of a galvanic cell (i.e. battery) Ecell always > 0!
(b) thermodynamic feasibility of a redox reaction (i.e. mixing) Ecell can be +ve, ve, 0
(LT
Strategy to solve Ecell calculation: Interpretation of Ecell:
(1) Determine what species are present Ecell > 0 (i.e. G < 0)
(2) Quote the relevant halfequations & 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] Ecell < 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 Ecell
Ecell = 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
rig
G = RT lnK RT
Ecell = lnK
nF
Thermodynamic where R = gas constant = 8.31 J mol1 K1
Feasibility T = absolute temperature (in K)
n = amount of electrons transferred
G Ecell F = Faraday constant = 96500 C mol 1
= H TS G = nFE
cell = Ered Eox G = Gibbs free energy change (in J mol 1)
Examples:
The reaction between I and S2O82 is energetically feasible (Ecell = +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 (Ecell = +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)
Co
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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
(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
rig
py
Co
X)
1 Predicting Products formed in an electrolysis (Qualitative)...
There will be selective reactions at the electrodes which is dependent on:
(LT
Note: If in aqueous phase, to consider water and compare E
Presentation of Answer
At anode, is more easily oxidised than as E ( ) is more negative than E ( ).
py
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.
Co
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 mol1)
L : Avogadro constant (6.02 1023 mol1)
e : charge of one electron (1.60 1019 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
Anodising of Aluminium
Purpose : increase thickness of corrosion–resistant Al2O3
layer on surface of Al metal
py
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
X)
1 Definitions:
Bronsted acid is a proton H+ donor. (Note: H+ is equivalent to H3O+.)
Bronsted base is a proton H+ acceptor.
(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
ht
OH BH
Define Kb : Kb ( B(aq) + H2O(l) OH(aq) + BH+(aq) )
B
rig
For conjugate acidbase 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).)
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.
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
(Adapted from past year JJC Physical Summary)
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
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)
py
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
Change x +x +x Change x +x +x
Eqm cas x x x Eqm cbs x x x
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])
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 40 Topic 16: Acids, Bases & Solubility Equilibria
(Adapted from past year JJC Physical Summary)
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
(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)
[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
rig
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).
py
Co
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 41 Topic 16: Acids, Bases & Solubility Equilibria
(Adapted from past year JJC Physical Summary)
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
4. Check and mark the buffer region (i.e. mixture of WA/WB and its
rig
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 ×
WASB 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)
SBWA titration: buffer region occurs after equivalence point
py
2.5 ×
0
Vneut vol /cm3
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 42 Topic 16: Acids, Bases & Solubility Equilibria
(Adapted from past year JJC Physical Summary)
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.
(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.
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 43 Topic 16: Acids, Bases & Solubility Equilibria
(Adapted from past year JJC Physical Summary)
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
2019 JPJC J2 H2 Chemistry (9729) / LeeTX 44 Topic 16: Acids, Bases & Solubility Equilibria
(Adapted from past year JJC Physical Summary)
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
(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.
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
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.
Si
electrical conductivity
Al Al
melting point /°C
Mg Mg
rig
Na Na
S8
Si
Cl2
P4 Ar P4 S8 Cl2 Ar
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)
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 lowlying vacant 3d orbitals
to expand octet structure.
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 lowlying 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)
12
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
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
(
nonmetallic 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
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)
\
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)
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).
Note: BeO is covalent with ionic character amphoteric oxide (diagonal relationship with Al2O3)
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.
(LT
Hence, the ability of M2+ to polarise the large anion decreases and the CO 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.
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).
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
HX Observations
HCl Does not decompose even when heated strongly
HBr Redbrown fumes of Br2 when heated strongly
HI Violet fumes of I2 obtained when a redhot 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)
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.
(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.
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).
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–
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.
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
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
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
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).
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+
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
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).
3.3 TE complexes and compounds are usually coloured due to dd 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
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.
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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.
(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
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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:
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S2O82(aq) + 2I(aq) 2SO42(aq) + I2(aq) Ecell = +1.47 V
Since Ecell 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
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.
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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.
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.
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Catalyst does not alter the enthalpy change of reaction.
SCN [Fe(H2O)5SCN]2+
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