Nanyang Junior College

J2 H2 Chemistry Remedial Programme 2018

CHEMISTRY SURE IMPROVE

Physical Chemistry
1. Stoichiometry , Redox and Gases
2. Chemical Bonding
3. Chemical Energetics
4. Reaction Kinetics
5. Chemical Equilibrium & Ksp
6. Ionic Equilibria
7. Electrochemistry

Compiled by:

Mr Chin De Shun Mr Goh Kien Soon

tf
Ms Lim Meilin
Nanvanq Junior College J2 H2 Chemistry 2018

H2 Chemistry Remedial Worksheet

Topics: Stoichiometry, Redox & Gases
Stoichiometry

Relative Masses
The relative atomic mass, Ar , of an element, is the weighted average mass of the
1
isotopes of the element compared to — the mass of a 12C
atom .
12

The relative isotopic mass of an isotope is the mass of an atom of the isotope compared

^
12C
to the mass of a atom. (Note: Isotopes are atoms of the same element having the
same atomic number but different mass number, i. e. same number of protons but different
number of neutrons)

The relative molecular mass, Mr , of an element or compound , is the weighted average

mass of a molecule of the element or compound compared to — the mass of a 12C atom.
12

The relative formula mass, Mr, of an element, is the weighted average mass of a
formula unit of the compound compared to — the mass of a 12C atom.
12

The Mole and Avoqadro Constant

One mole of substance is the amount of substance that contains as many particles as
there are carbon atoms in exactly 12 g of 12C.
Units : mol
(The number of carbon atoms in 12 g of 12C is found to be the Avogadro constant, L =
6.02 x 1023)

N
n=—
L
where n = amount of substance in mol
N = number of particles
L = Avogadro constant
m
n=—
M
where n = amount of substance in mol
m = mass in g
M = molar mass in g mol-1

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Formulae
Empirical and Molecular
The empirical formula of a compound is the simplest formula that shows the relative
number of atoms of each element present in a compound.

The molecular formula of a compound is the formula that shows the actual number of
atoms of each element present in one molecule of a compound.

Composition by Mass Data

When given composition by mass data, the following table will be useful in determining the
empirical formula of the compound:

Element X Y
Composition by mass / g
OR
Composition %
Amount / mol
Divide by smallest number
Simplest ratio

Stoichiometric Calculations

How to determine the limiting reagent?

Step 1: Write out the balanced equation for the reaction so as to determine the mole ratio
of reactants and products.

Step 2: Convert the masses (or any other quantities) of the reactants to amount in moles.

Step 3: Use the mole ratio (from Step 1) to determine which reactant produces the
smallest amount of product. This reactant is the limiting reagent.

Theoretical, Experimental and Percentage Yield

Actual Yield
Percentage Yield = x 100%
Theoretical Yield

Reacting Gas Volumes

At standard temperature and pressure (s.t.p.): 273 K [0 °C] and 105 Pa [1 bar]
Vm = 22.7 dm3

At room temperature and pressure (r.t.p.) : 293 K [20 °C ] and 101325 Pa [1 atm]
Vm = 24 dm3

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The amount of a gas can be found , given the volume of the gas :

V
Vm
where n = amount of substance in mol
V = volume of the gas
Vm = molar gas volume (depending whether it is at s.t.p. or r.t.p.)

Combustion Analysis
Compounds that contain only C and H (sometimes with 0) can be determined using
combustion analysis.

CxHyOz
H2O removed by
H2O
Combustion * drying agent (e.g.
+ * + phosphorous(V)
oxide, P4O10)
O2 (excess) C02

Products pass through

two U-tubes.
CO2 removed by
alkalis (e.g.
NaOH)

Eudiometry
The molecular formula of an unknown gaseous hydrocarbon may be found using
eudiometry.

CO2
Gases * Instead of
CxHy Combustion removed
remaining: removing
+ by alkali
02 * O2
(e .g.
CO2 with
(unused ) alkali,
(excess) NaOH) O2
+
( unused) alkaline
CO2 * pyrogallol
Steam is condensed can be used
to water hence its to remove
volume is negligible . O2 .

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General equation for combustion:

CxHy + ( X +

^ ) C>2 XCO2 + H 2O
~

Use mole ratio to determine x:

Vco 2
x
V,CXH, 1

Determine the volume of oxygen used:

V0 (used) = V0z (excess ) - V02 (unused )

Use mole ratio to determine y:

V02 (used ) _ x

VC„ Hy 1

Calculations Based on Solutions

The concentration of an aqueous solution may be stated as
mass of solute (g) m
(i) mass concentration (g dm 3) =
volume of solution (dm5 ) V
amount of solute (mol) _ n
(ii) molar concentration (mol dm"3), c =
volume of solution (dnf ) V

Dilution
When a solution is diluted (by adding more solvent) , the concentration of the solution
decreases but the amount of solute in the diluted solution remains unchanged .

Amount of solute before dilution = Amount of solute after dilution

C1V1 = C2V2

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Redox

Oxidation and Reduction

Oxidation Reduction
Gain in Oxygen Loss of Oxygen
Loss of Hydrogen Gain in Hydrogen
Loss of Electrons Gain in Electrons
Increase in Oxidation number Decrease in oxidation number

Oxidising and Reducing Agents

Oxidising Agents Colour Reduced to Colour

Mn04~ (acidic) Purple Mn2+ Colourless
Mn04~ Purple Mn02 Brown/Black ppt
(alkaline/neutral)
Cr2072 (acidic)
'
Orange Cr 3+ Green
I03 Colourless 12 Yellow/Brown
12 Yellow/Brown r Colourless
Fe 3+ Yellow (aqueous Fe2+ Green
ions)
H2O2 Colourless H20 Colourless

Balancing Redox Eguations

How to write balanced half-equations in acidic medium:
Example: Write the half-equation for the reduction of manganate(VII) ions to manganese(ll)
ions in acid medium.

Steps Half-equation
1. Write skeletal half-equations and
balance the atoms being Mn04- -> Mn2+
oxidised/reduced.

2. Balance O atoms by adding H2O. MnCV -» Mn2+ + 4H20

3. Balance H atoms by adding H+. Mn04 + 8H+ -» Mn2+ + 4H20
‘

4. Balance charges by adding

electrons . MnCU- + 8H+ + 5e~ Mn2+ + 4H20

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How to write balanced half-equations in alkaline medium:

Example: Write the half-equation for the reduction of manganate(VII) ions to
manganese(IV) oxide in alkaline medium.

Steps Half-equation
.
1 Write skeletal half-
equations and balance the
atoms being Mn04 -» MnC> 2
"

oxidised/reduced.

2. Balance O atoms by adding

H20. Mn04 Mn02 + 2H20

3. Balance H atoms by adding

H+. Mn04 + 4H+
"
Mn02 + 2H20

4. Balance charges by adding

electrons. Mn04 + 4H+ + 3e
" "
Mn02 + 2H20

.
5 Neutralise H+ by adding
OH to convert them into
"
Mn04 + 4H+ + 40H + 3e -» Mn02 + 2H20 + 40H
" " " "

H20. (Remember to add the

same number of OH on "
Overall:
either sides of the half- Mn04 + 2H20 + 3e
”
Mn02 + 40H
” ”

equation)

How to write balanced redox equations in acidic/alkaline medium:

1. Write balanced half-equations for the two reacting species as though they are in an
acidic medium.

.
2 Multiply each half-equation to make the number of electrons equal.

3. Combine the two half-equations. Simplify if necessary.

4. Change to alkaline medium by neutralising H+ with OH if required. "

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Gases
Boyle’ s Law
When n and T are constants

1
V oc -
P

The product pV is a constant.

pV = constant
P1V1 = P2V2

Charles’ Law
When n and P are constants

V oc T

The quotient of V and T is a constant.

V
= constant
T
V, _ V2
T1 T2

Avoqadro’s Law
When T and p are constants

V oc n

The quotient of V and n is a constant.

V
= constant
n
V, _ V2
n2
1
"

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Ideal Gas Equation

By combining the above gas laws, an ideal gas equation can be derived.

pV = nRT

Units to be used:
Pressure, p: Pa or Nm 2 Amount, n: mol

Volume, V: m3 Temperature, T: K

*lf any of the units is not followed, the values used will not give a balanced equation.

Note the following conversions!

Temperature, T: X °C = (X + 273) K
Pressure, p: 1 atm = 101325 Pa = 760 mmHg
Note: AT (in K) = AT (in °C) BUJ
T (in K) T (in °C)
Volume, V: 1 dm3 = 1000 cm3 = 10 3 m3
1 cm3 = 10 6 m3 “
*
Dalton’s Law

PT - PA + PB + ...
where pi = total pressure of the gas
PA, PB, ... = partial pressures of constituent gases

Partial Pressures
Partial pressure of a gas in a mixture is given by:

PA = Xh x PT
= nA X P T
nT
where %A = mole fraction of the gas A in the mixture

By using Avogadro’s Law, mole fractions can also be substituted by volume fractions.

pA = volume fraction of gas A x pT

vA X PT
VT

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The Kinetic Theory of Gases

Two important basic assumptions of the kinetic theory as applied to an ideal gas :

1. The gas particles do not exert any forces of attraction on each other.

2. The volume of the gas particles is negligible compared to the volume of the
container.

Conditions for Ideal Gas Behaviour

1. Low Pressure
At low pressures, the volume of gas particles is insignificant compared to volume of
container .

At high pressures, gas particles are packed closer together. The volume of gas particles
becomes significant relative to the volume of container.

2. High Temperature
At high temperatures, gas particles have sufficient kinetic energy to overcome the weak
intermolecular forces of attraction.

At low temperatures, gas particles have less kinetic energy and will move slower, and
hence collide with one another with less force. This makes the intermolecular forces of
attraction more significant.

Hence , a real gas shows the greatest deviation from ideal under high pressure and/or
low temperature .

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Sketching of graphs

E.g. Sketching graphs of p against 1/V and pV against V

(mass of gas and temperature are kept constant)

Step 1: Using the ideal gas equation, make the variable in the y-axis the subject (i.e.
place it on the left-hand side).

Example 1 Example 2
P against 1/V: pV against V:
pV = nRT pV = nRT
p = nRT/V

Step 2: On the right-hand side, separate the constants from the variable in the x-axis.
(If the variable in the x-axis does not exist on the right-hand side after step 1, the
graph is a horizontal line parallel to the x-axis.)

p against 1/V: pV against V:

p = (1/ V)(nRT) pV = nRT (graph is a horizontal line parallel to the x-axis)

constant constant

Step 3: Write the proportionality between the variables in the y and x-axes, then sketch
the graph according to the proportionality.

P against 1/V: pV against V:

p oc 1/V

P pv
“

0 0
MV V

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H2 Chemistry Remedial Worksheet

Topic: Chemical Bonding

Types of chemical bonds

Chemical Bonds

Intramolecular bonds Intermolecular bonds

( strong) ( weak)

ionic bonds covalent bonds metallic bonds van der Waals forces hydrogen bonds

Permanent dipole - Instantaneous dipole -

permanent dipole forces induced dipole forces
Intramolecular bonds

1) Ionic Bonding (i.e. in sodium chloride , NaCI)

• Formation of ions in such compounds involves a complete transfer of one or more

electrons between atoms .
• Ions in these compounds are held together by ionic bonds which involve an
electrostatic attraction between oppositely charged ions . (i.e. Na+ and Cl ions)-

• Typically formed from a metallic element and a non-metallic element due to the
great difference in their electronegativities.

Strength of ionic bonding

• Magnitude of lattice energy is given by

z+ z
LE oc
(r + r)
Where z+ and z are the charges on the cation and anion respectively
“

and r+ and rare the ionic radii of the cation and anion respectively.
• Strength of ionic bonds increases with
o Greater ionic charges
o Smaller ions (smaller interionic distance)

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2) Covalent bonding

Each atom achieves a full valence shell of electrons by sharing electrons.

Difference in electronegativity of the two atoms is small.

XX XX
H« + x Cl x
x
XX
H * Cl
XX
*
The electron pair involved in bonding is called the bond pair or shared pair .

The electron pair not involved in bonding is called the lone pair or unshared pair.

Therefore, for HCI, there are altogether 1 bond pair and 3 lone pairs of electrons.

Formation of a and n bonds

o bond: head-on overlap (collinear overlap)

CT

o n bond: side-way overlap (collateral overlap)

a bond can be overlap of: n bond is the overlap of p orbitals

(A) s + s orbitals
+ >
0*0 GO
(B) s + p orbital

O * oo — Oxo
(C) p + p orbitals

OO + OO
— CXXXD

o For single bond , it consists of one a bond, zero n bond.

o For double bond , it consists of one a bond , one n bond
o For triple bond, it consists of one a bond, two n bonds.

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Factors affecting bond strengths:

Bond strength is dependent on 2 factors:

• Extent of orbital overlap between two bonded atoms.

o Larger the degree of overlap, stronger the bond
• How strongly electrons in the overlap region are attracted to the nuclei of the atoms.
o Stronger the attraction, stronger the bond

Dot-and-cross diagrams for neutral ( uncharged ) molecules

1. Determine the correct number of valence electrons for each atom (from the Group
no.)
2. Guess the connectivity of the atoms in the molecule, i.e. which atom is bonded to
which.
Note: For acids, e.g. H2SO4, the acidic protons are bonded to oxygen not sulfur.
3. Identify the central atom (not H) . There can be more than one central atom.
• If central atom is a Period 2 element,
o Maximum is octet, i.e. total of 8 electrons around central atom
• If central atom is Be, B or Al
o May not be able to obtain an octet unless dative bond
o It can be an electron deficient molecule
• If central atom is N
o Check total number of valence electron from all atoms .
If even number, octet usually possible
If odd number , give N 7 e and give the rest of the atoms octet
*

Odd electron molecule

• If central atom is Period 3 element and below,
o Expand octet where possible; avoid use of dative bonds.

Note:

> Try to give the non-central atoms an octet.

> Use single bonds first to get an octet for each atom. If not possible, use double bonds
and triple bonds. Finally , use dative bonds.

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Dot-and-cross diagrams for polyatomic ions

Polyatomic cations

Strategy
XH+ X + H+ -> XH+ (acid-base reaction)
e.g. NH4+, HSO+ e.g. NH3 + H+ NH4+
e.g. H2O + H -> HsO+
+ ^
1. Draw dot-and-cross diagram for X.
.
2 Draw dot-and-cross diagram for XH+ using a lone pair of
electrons on one of the atoms in X to form a dative bond to H+.

Y+ ( others)
_
Y -> Y+ + e (loss of e from neutral parent molecule)
~

e .g. BrF2 BrF2+ + e ~

1. Draw dot-and-cross diagram for neutral parent molecule Y.

2. Draw dot-and-cross diagram for Y+ by removing e from the
~

least electronegative atom.

Polyatomic anions

Strategy
Oxoanions Remove H+ from parent acid molecule ,

e.g. NO3 , NO2 e.g. HNO3 H+ + N03-

COs2 , HCO3-,
-
e.g. HNO2 -> H+ + N02-
SOs2-, HSOs , -
»
e.g. H2SO4 - H+ + HSO4-
S042 , HSO4
- -
e.g. H2SO4 -> 2H+ + SO42-

.
1 Draw dot-and-cross diagram for parent acid molecule (there
should be at least one O-H and the O atoms are usually bonded
to the central atom)
.
2 Draw dot-and-cross diagram for oxoanion by removing H+
from O in parent acid molecule. The extra electron is then on the
O atom which has lost the H+.

Y ( others)
“
Y + e -> Y (gain of e from neutral parent molecule)
~ ~ ~

e.g. ICI4 + e -> ICU-

~

1. Draw dot-and-cross diagram for neutral parent molecule Y .

2. Draw dot-and-cross diagram for Y by adding
~
to the most
electronegative atom.

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• Exceptions to octet rule for covalently bonded species

Types of exception Examples

1. Electron deficient molecules
Central atom has an incomplete octet.
Usually contain Group 2 atoms (most common example is
Be) or Group 13 atoms (e.g. B, Al) as the central atom
•• ••
ci XAI * ci
•• X
x
••
: . :
sci:
••
2. Odd electron molecules (free radicals)
Central atom has an odd number of valence electrons, so O . xx
:N:;O
,

they cannot have all their electrons in pairs.

XX
o called free radicals, containing a lone (single
unpaired) electron, making them extremely
reactive.
3. Expanded octet
Many molecules and ions with 8 valence electrons :CI: :•ci••:
around the central atom. ••,^ \
Only central non-metal atoms from Period 3 onwards can
expand their octets.
o Due to the ability to accommodate additional
electrons using empty d orbitals in addition to s and
:c * x + ci
|
•• \ ••*
:CI:
,
-
p orbitals.
••
Period 2 elements cannot expand their octets.
o Absence of d orbitals and they will need to use
energy orbitals in the third shell which is
energetically unfavourable .

Shapes predicted by VSEPR theory

No of No. of bond No. of lone Shape Bond angle/ 0

electron pairs pair of pair of

electrons electrons
2 2 0 Linear 180
3 0 Trigonal planar 120
3 2 1 V-shaped / Bent 118
4 4 0 Tetrahedral 109.5
3 1 Trigonal 107
pyramidal
2 2 V-shaped / Bent 105
5 5 0 Trigonal 90 (axial)
bipyramidal 120 (equatorial)
4 1 See-saw <90 (axial)
<120 (equatorial)
3 2 T-shaped 88
2 3 Linear 180
6 6 0 Octahedral 90
5 1 Square pyramidal 90
4 2 Square planar 90

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Steps to determine whether a molecule is polar or non-polar

1. Draw the dot-and-cross diagrams of the molecule.

2. Use VSEPR theory to draw the shape of the molecule.
3. For each bond, draw the bond dipole (arrow from less electronegative atom to more
electronegative atom).
• Bond dipole arises from the difference in electronegativities between the two
atoms.
• Polar bond can be represented using the symbols 5+ and 5-.
• Bond dipole can be represented using > notation. The crossed end
represents the positive end of the dipole.
4. Find the net dipole (vector sum).
5. If there is no net dipole, the molecule is non-polar ; otherwise it is polar.

3 ) Metallic bonding
• Electron-sea model: metal -> an array of metal cations in a sea of delocalised
valence electrons

free electrons from outer

shells of metal atoms

metal ions

• Electrostatic attractions between the positive cations and the negative

delocalised electrons constitute the metallic bonds .
• Metallic bond strength increases with number of valence electrons.
• Limitation to the electron-sea model: the model cannot explain why Cu, which
has more valence electrons than Cr, has the lower melting point.

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4) Intermolecular bonding

a ) Permanent dipole - permanent dipole (pd pd ) forces of attraction

-

• Present in polar molecules

• Positive end of one molecule’s dipole can attract the negative of another molecule’s
dipole

b) 2. Instantaneous dipole - induced dipole (id-id ) forces of attraction

• Present in both polar and non-polar molecules
o Non-polar molecules: Only id-id forces of attraction are present ,
o Polar molecules: Both id-id and pd-pd forces of attraction are present.

c) Hydrogen bonding

Conditions for two molecules to form a hydrogen bond between the two of them:

• One molecule must have a H atom bonded to a highly electronegative atom (F, O
N) .
• The other molecule must have at least one lone pair of electrons on a highly
electronegative atom (F, O , N).

hydrogen bond

5- 5+
X-H

X, Y = N, 0 or F

Consequences of hydrogen bonding

• Anomalously high boiling points of ammonia , water and hydrogen fluoride

o Boiling point of H2O > HF > NH3
o H2O is able to form two hydrogen bonds per molecule in water, while HF and
NH3 can form on average one hydrogen bond per molecule ,

o More extensive hydrogen bonding in H2O -> highest boiling point

o H-F bond is more polar than N-H -> Boiling point of HF > NH3
• Hydrogen-bonded dimers
o Mr of ethanoic acid found to be 120 instead of 60 at temperatures just above
its boiling point and when it is dissolved in non-polar organic solvents .
• Intramolecular hydrogen bonds
o Melting point of 2-nitrophenol lower than 4-nitrophenol
o 2-nitrophenol forms less extensive intermolecular hydrogen bonding as
compared to 4-nitrophenol, due its ability to form both intramolecular and
intermolecular hydrogen bonding.
• Density of ice and water
o Density of ice < liquid water

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To explain for differences in melting and boiling points of simple molecular compounds

Compare Mr

Similar Mr ? Different Mr ?
Compare types of IMF a. large polar Polar molecule (sufficiently large)
or non-polar id-id forces > the p.d - p.d
a. IMF are H bond > p.d - p.d > id-id
molecules forces.
different (strongest) ( weakest )
4 Compare the strength of
b. hydrogen Compare dispersion forces .
bonds (i) Average number of hydrogen bonds per Molecule of the largest size (more
molecule and electrons, more polarisable)
(ii) The electronegativity of atom -> Strongest dispersion forces.
c. permanent Most polar molecule strongest p.d - p.d forces.
Note:
dipole-dipole
forces (polar
•I id-id forces and p.d. - p.d.
forces are present in polar
molecules)
molecules.
d. instantaneous Larger surface area of contact between molecules • Polar molecule is small o.d. -
dipole - induced Stronger id-id forces. p.d. outweigh id-id forces
(non-polar Elongated molecule > spherical molecule • Polar molecule Is big id-id
molecules )
(strongest) (weakest) forces outweigh p.d. - p.d.

b. small p.d. - p.d. forces between the small

polar polar molecules may be weaker than
molecule vs the id-id forces between the
large non- large molecule
polar
molecule

5 ) Ion- dipole interactions

• Electrostatic forces of attraction between an ion and a polar molecule.

• Example: hydration

5+
5+
H

5+
5+ H
H
0

Ion-dipole interactions for Ion-dipole interactions for

sodium ion in aqueous chloride ion in aqueous
solution solution

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Physical Properties

A. Melting point/boilinq point

When asked to account for differences in melting point/boiling point

You are to include in your answer:

1. Structure

2. Type of bonding

3. Particles involved

4. Amount of energy required to overcome bonding

Type of structures , bonding, particles, amount of energy required

1.Structure 2.Bonding 3.Particles 4.Amount of Example

energy
required
Giant metallic Strong metallic Cations and Large Na
bonds sea of
delocalised
valence
electrons

Giant ionic lattice Strong ionic Oppositely Large KCI

bonds charged ions
Giant covalent/ Strong covalent Atoms Large Diamond, Si
molecular bonds in the 3D Si02
network
Giant layered Strong covalent Carbon atoms Large Graphite,
bonds boron nitride
‘Simple molecular Instanaenous Molecules Small C02, PCI5
dipole - induced
dipole forces of
attraction

Permanent Polar HCI

dipole - dipole molecules or
forces of molecules
attraction
Hydrogen Molecules H20, HF, NHS
bonding

* to compare the strength of forces between instantaneous dipole - induced dipole forces
of attraction / permanent dipole - permanent dipole forces of attraction / hydrogen bonds
(Refer to page 8)

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Example:

Cis-1 , 2-dichloroethene Trans-1, 2-dichloroethene

Boiling point/ °C 60.2 (higher) 48.5
Melting point/ ° C -81.5 -49.4 (higher)

The cis isomer of 1,2-dichloroethene has a higher boiling point of 60.2°C than the trans
isomer of 1,2-dichloroethene, which has a boiling point of 48.5°C.

While the cis isomer has a lower melting point (-81.5°C) than the trans isomer (-49.4°C).

Explain why.

Both compounds have simple molecular structures.

The cis isomer has permanent dipole - permanent dipole (pd-pd) forces of attraction
between its molecules. The trans isomer has weak instantaneous dipole - induced dipole
(id-id) forces of attraction between its molecules.

More energy is required to overcome the stronger pd-pd forces of attraction in the cis
isomer than the weaker id-id forces of attraction in the trans isomer.

Hence, the cis isomer has a higher boiling point than the trans isomer.

However, the molecules in the trans isomer can pack closer together in the solid lattice.
This results in stronger id-id forces of attraction. More energy is required to overcome the
stronger id-id forces in the trans isomer , leading to its higher melting point.

B. Electrical conductivity

• Ability to conduct electricity depends on the presence of

o Mobile ions
o Mobile electrons
• Ionic compounds does not conduct electricity in solid state but conducts when
molten or in aqueous solution
o Solid state: Ions are not mobile; held in fixed positions by strong electrostatic
forces. No mobile electrons to act as charge carriers,
o Molten/aqueous state: Charge carriers are mobile ions .
• Metallic compounds conduct electricity due to presence of mobile delocalised
valence electrons which act as charge carriers under an applied potential difference.
Example: Graphite conducts electricity.
o Each carbon atom uses three valence electrons to form three a bonds with
three other carbon atoms. The fourth valence electron is in a 2pz orbital,

o These electrons can carry charge along each layer.

o Graphite conducts electricity along the axis parallel to the layers but not
perpendicular to the layers.

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C. Solubility

• Ionic compounds are soluble in polar solvents such as water but insoluble in
non-polar solvents such as CCU.
o In polar solvent: Energy released through strong ion-dipole interactions
compensate for the energy needed to break the ionic bonds in the solid
lattice.
o In non-polar solvent: Non-polar solvent molecules are held together by weak
instantaneous dipole - induced dipole forces of attraction, which is smaller in
magnitude than the forces between ions in an ionic crystal. Energy released
from ion-solvent interactions cannot compensate for the energy required to
overcome the strong ionic bonds between ions. So the solvent molecules
cannot solvate the ions.

• Simple molecular structures are soluble in non-polar solvents, insoluble in polar

solvents.
• Simple molecular structures that are able to form hydrogen bonding
o Soluble in water due to the ability to form hydrogen bonding with water

• Giant molecular structures are insoluble in all solvents .

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NYJC/Promo 2008 H1/11

5 What are the bond angles of x, y and z in the molecule below?

CH3 o H
X

H3C^C N z

H
H
X y z
A 90° 109° 120°
B 107° 120° 109°
C 120° 90° 109°
D 109° 120° 107°

HCI/Prelim 2007/1/31

6 The compound sodium borohydride , NaBhU, is commonly used as a source of the

hydride anion for synthetic purposes . Which of the following types of bonding are
found in the compound?

1 Ionic
2 Covalent
3 Hydrogen bonding

MJC/Prelim 2007/1/9

7 Nudic acid B is an acidic antibiotic isolated from the culture medium of the
basidiomycete Tricholoma nudum (Bull.) Fr.

O — C — CH=CH — C — C —C — C — C=N
OH

Nudic acid B

What is the number of a and n bonds present in the molecule?

a n
A 16 5
B 13 8
C 13 5
D 10 8

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MJC /Prelim 2007/1/11

8 Solid X has the following properties.

• It is insoluble in tetrachloromethane and water.

• It melts at 2730 °C .
• It is a non-conductor of electricity.

Which of the following is a likely identity for X ?

A Rubidium chloride
B Lithium
C Graphite
D Boron nitride

MJC/Prelim 2007/1/32

9 Beryllium difluoride reacts readily with trimethylamine, (CH3)3N to form a stable

addition product. Nitrogen trifluoride has no reaction with trimethylamine.

Which of the following statements are true?

1 Nitrogen trifluoride does not react as the nitrogen atom lacks energetically
accessible orbitals for reaction.
2 The bond angle in the addition product is 109.5°
3 The molar ratio for the reaction between beryllium difluoride and (CH3) 3N is
1: 1.

SAJC/Promo 2006/ 2/2

10 (a) AIF3 has high melting point of 1275 °C and AlCb has melting point of only
-150 °C.
(i) Draw the dot-and-cross diagrams to illustrate the bonding in AICI3 [2 ]
and AIF3.

(ii) Identify the type of bonding present in AIF3 and AICI3. [1]
(Mi) Explain the difference in the melting point between AIF3 and AlCb. [ 2]
( iv) State the difference in one other physical property (besides melting
and boiling points) for the two compounds, AIF3 and AlCb. [1 ]
(b ) ( i) Aluminium chloride catalyses certain reactions by forming
carbocations, C 2Hs+, with chloroethane as shown in the following
equation.
C 2H5CI + AlCb -» C2H5+ + AlCb"

Explain, in terms of bonding, how AICU is formed.

~
[2 ]

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H2 Chemistry Remedial Worksheet

Topic: Chemical Energetics

Part 1: Enthapy

Endothermic process is where heat is absorbed from the reaction mixture to the
surroundings, leading to a decrease in surrounding temperature . Products have a
higher enthalpy (energetically less stable) than reactants. Enthalpy of the system
increase. AH has a positive sign.

Exothermic process is where heat is evolved from the reaction mixture to the
surroundings, leading to an increase in surrounding temperature . Products have a
lower enthalpy (energetically more stable) than reactants. Enthalpy of the system
decreases. AH has a negative sign.

Standards Conditions

(a) Temperature at 25 °C or 298 K

(b) Pressure at 1 bar or 105 Pa

(c) Substance in the most stable physical/allotropic form .

For instance, H2(g) exists normally as a gas at standard conditions.

Na(s) exists normally as a solid at standard conditions.

For carbon which can exist as graphite or diamond , graphite is chosen as the
standard as graphite is the most stable form of carbon at standard conditions.

(d) Solution concentration is 1.0 mol dm-3

Note: A substance at its most stable physical state at 25 °C and 1 bar is said to be at
standard state.

Definition of Terms

The standard enthalpy change of a reaction. AHre, is the heat energy absorbed or
evolved when molar quantities of reactants as stated in the thermochemical equation
react together under standard conditions.

For example,
2H2(g) + 02(g) - 2H20(I) AHre = - 572 kJ moF1
*
H2(g) + 1/2 02(g) -> H20(l) AHre = 1/2 (- 572) = - 286 kJ mol-1
mcAT
AHr = + amount of limiting reagent (for endothermic reaction)
mcAT
AHr = “ amount of limiting reagent (for exothermic reaction)
where m is the mass of solution, c is the specific heat capacity and AT is the change of
temperature.

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The standard enthalpy change of combustion , AHC9 is the energy change when one
mole of a substance is completely burnt in excess oxygen under standard conditions.

AHce is usually negative .

For example C2H6(g) + 02(g) -+ 2C02(g) + 3H20(I) AHce = -1560 kJ mol 1'

The standard enthalpy change of neutralisation . AHne, is the energy change when one
mole of water is formed during the neutralisation of an acid and an alkali under
standard conditions.

AHn9, is always negative .

For example, NaOH(aq) + HCI(aq) -> NaCI(aq) + H20(l) AHne = -57.3 kJ mol-1
AHn9 for a strong acid and strong base is nearly constant at -57.3 kJ mol-1. For
neutralization involving weak acids or weak alkalis, AHn9 differs significantly from
-57.3 kJ mol-1.

mcAT
AHn = amount of limiting reagent
where m is the mass of solution , c is the specific heat capacity and AT is the change of
temperature.

The standard enthalpy change of formation, AHf9 is the energy change when one mole
of a compound is formed from its constituent elements in their standard states under
standard conditions.

AHf9 can be positive or negative.

AHf9 of an element is always zero .

For example, H2 (g) + !402 (g) H20(l) AHf9 = - 286 kJ mol-1

Important formula: AHr9 = £nAHf9 (products) - XmAHf9 (reactants)

The bond dissociation energy , AHdiss9 is the energy required to break one mole of
covalent bond between two atoms in the gaseous state .

Hdiss9 is always positive .

For example HCI(g) -> H(g) + Cl(g) AHdiss9 = +431 kJ mol-1

Calculations using bond energies only give approximate answers. Bond energies quoted
in the Data Booklet are average values from many different molecules that contain that
particular bond.

Important formula: AHr9 = £BE(bonds broken) - £BE(bonds formed)

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The standard enthalpy change of atomisation. AHat ® is the energy change when one
mole of gaseous atoms is formed from its element under standard conditions.

AHat ® is always positive .

For example , Na(s) -> Na(g) AHat ® of Na(s) = +108 kJ mol-1

The first ionisation energy is the energy change when one mole of electrons is
removed from one mole of gaseous atoms to form one mole of gaseous singly
charged cations .

Ionisation energies are always endothermic .

The first electron affinity is the energy change when one mole of electrons is added to
one mole of gaseous atoms to form one mole of gaseous anions.

1st EA is usually negative while 2nd EA is positive .

For example 0(g) + e- -» O-(g) 1st EA = -141.4 kJ moF1

O-(g) + e~ -> 02-(g) 2nd EA = +790.8 kJ mol 1
”

The standard lattice enthalpy. AHiatt ® is the energy change when one mole of an ionic
compound is formed from its constituent gaseous ions at standard conditions.

Lattice energies are always exothermic .

For example, Na+(g) + Ch(g) -» NaCI(s) LE = -776 kJ mol 1

"

|LE| a iz
+
zn
r+ + r

The greater the ionic charge, the greater the magnitude of LE. The smaller the ionic
radius, the greater the magnitude of LE.

The standard enthalpy change of hydration . AHhyd® is the energy change when one
mole of gaseous ions is surrounded by water molecules , forming a solution at
infinite dilution under standard conditions.

AHhyd® is always exothermic .

|AHhyd®| a y the greater the charge or smaller the radius of the ion, the greater the
magnitude of AHhyde

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The standard enthalpy change of solution , AHsoi9 is the enthalpy change when one
mole of compound is dissolved by solvent (usually water ) such that further dilution
produces no more heat change under standard conditions.

AHsoi9 can be endothermic or exothermic .

AHsoi9 of a salt is highly endothermic , then the salt is unlikely to be soluble.

AHsoi9 of a salt is exothermic , then the salt is soluble.

Important formula: AHsoi9 = AHhyd9 - AHiatt9

If AHhyd9 > AHiatt9, then AHsoi9 is exothermic , the salt is relatively

soluble in water.
If AHhyd9 < AHiatt9, then AHsoi9 is endothermic, the salt is relatively
insoluble in water.

Hess' Law states that the enthalpy change for a chemical reaction is the same
regardless of the route the reaction takes , provided the initial states of the reactants
and the final states of the products are the same.

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Nanvanq Junior College J2 H2 Chemistry 2018

Part 2: Entropy and Gibbs Free Energy Change

Entropy , S , is a measure of the order of a system

Entropy change, AS , of a system AS = Sfinai - Sinitiai Units = J K ~ 1 mol 1

AS > 0 means entropy increase while AS < 0 means entropy decrease.

Factors affecting the entropy of the system

(1) Temperature

An increase in the temperature of a system leads to increase in entropy of the system as

there are more ways to distribute the energy quanta among particles. As a result, the
system becomes more disordered , entropy increase.

( 2) Change in phase

The change from solid to liquid to gas involves molecules having a more disordered or
random arrangement within the chemical system. Hence entropy increases (AS > 0) .

(3 ) Change in number of particles (especially gaseous systems)

The greater the number of molecules, the more random and disordered the system
becomes. There are more ways of arranging the molecules. Hence entropy increases
when the number of gas molecules increases .

(4) Mixing of particles

Mixing of gases, mixing of liquids and dissolving of solids increases the entropy (AS > 0) .

(5) Change in volume of gases

A gas spontaneously expands to occupy the whole container. Expansion of volume leads
AS > 0.

Gibbs Free Energy Change , AGe = AHe - TASe where T is temperature (in Kelvin)

AGe < 0 Reaction takes place spontaneously

AGe > 0 Reaction cannot take place spontaneously
AGe = 0 Reaction reaches equilibrium

Sometimes even if reaction is predicted to be feasible (i. e. AGe < 0), the reaction may be
too slow, as AGe tells nothing about the height of activation energy barrier.

Sign of
Remarks
AHe AS6
+ Reaction feasible at all temperature
+ Reaction not feasible at all temperature
+ + Reaction feasible at high temperature
Reaction feasible at low temperature
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H2 Chemistry Remedial Worksheet

Topic: Reaction Kinetics

Rate of Equation

change in concentration
rate =
change in time
Units: mol dm 3 time 1, where time can be in seconds, minutes or hours.
' '

The Rate Equation

For a general reaction aA + bB -» products, the rate equation is:

rate = k[ A]m[B]n
where [ ] = concentration in mol dm-3
m and n = order of reaction with respect to reactant A
and with respect to reactant B
k = rate constant

Orders of Reaction
For the stoichiometric equation aA + bB products, rate = k[A]m[B]n.

The powers, m and n , represent the orders of reaction with respect to reactant A and with
respect to reactant B.

The overall order is the sum of the individual orders, i.e. overall order = m + n

Note: a # m and b / n unless the reaction is elementary (i.e. a single step reaction).

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For a reaction A -» B
Order of Zero order 1st order 2nd order
reaction
Rate
equation rate = k[ A] = k ° rate = k[ A ] rate = k[ A]2
[ A ] vs time [Ak tAJf Rate [A]
Rate x = gradient is not x Rato
= constant gradient constant s gradient is not constant
s k

YzX ViX
u
-- V x VAX
*
0 o
Fnfe time
0 ti t2
[B] vs time [B [B] [B]
y - y

V« y V4 Y

V y
^

o a
X
0 *
time Y
t, 2 r time
ti t!
time

Half-life Half-life is constant.

Half-life is not constant
Half-life is not constant as it increases with
ti = t2 time.
as it decreases with
time. In 2
t1
2 k ti * t2
Rate vs [A ] rate

rate
rate

Gradient = k

"J

Gradient « k
0 K
[ ]

*
[ A] Rate is directly
Rate is independent of proportional to [A] ,

[ A ] When [A] changes,

, When [A] changes by a
0
rate remains constant. factor n , rate changes [A ]2
by the factor n. Rate is proportional to
the square of [ A] ,

When [A] changes by a

factor n , rate changes
by the factor n2 .
Units of
rate mol dm-3 time-1 time-1 mol-1 dm3 time-1
constant
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Rate Constant, k
• When temperature increases, k increases.
• When a catalyst is introduced, k increases.
Deducing Orders of Reaction from Experimental Data

1. Calculation/lnspection Method
When given a table of data with concentrations of reactants and initial rates, the orders of
reaction with respect to the reactants can be deduced by calculation/inspection.

Note: If time is used instead of initial rate, the relative rate may be calculated by taking
1 1
. This is because rate oc when the concentration of the reactant can be taken
time time
as a constant.

E.g. For A + B + C -» products

3 3
[A] / mol dm 3 [B] / mol dm '
[C] / mol dm
'
relative rates
0.01 0.01 0.01 1
0.02 0.01 0.01 2
0.01 0.02 0.01 1
0.01 0.01 0.03 9

When [ A] doubled from 0.01 to 0.02 mol dm 3, the rate doubled (2/1 = 2) . Hence, it is first
'

order with respect to A .

When [B] doubled from 0.01 to 0.02 mol dm-3, the rate remained constant. Hence, it is
zero order with respect to B .
When [C] tripled from 0.01 to 0.03 mol dm 3, the rate increased by 9 times (9/1 = 9).
'

Hence, it is second order with respect to C .

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 Nanvanq Junior College J2 H2 Chemistry 2018
M

2. Half-life Method

Type of [Ak W* Rate [A]

graph Rate x = gradient is not x Rate
= constant gradient constant = gradient is not
=—k constant

VlX
I
y« x y« x

0v a o a
0 Tinte A
v time
ti t2
time
ti
How to
deduce [ A] decreases linearly Half-life is constant,
i.e. t = t = t 2 , , Half-life is not constant,
with time.
2 i.e. t t 2 ,*
Rate is independent of First order with
[A ] . respect to A. Cannot confirm its
order of reaction with
Zero order with In 2 respect to A. (Another
t1 method is required.)
respect to A . 2
k

3. Product-time Curves

Type of [Bk
IB]
IB] 4 y --
graph y
y4 y
v« y
%y
^y

o ot
o time T
X Y time
tl
«t ,
t
How to
deduce [B] decreases linearly Half-life is constant ,

with time. i. e. t = t = t 2 , , Half-life is not constant

i.e. t t 2 ,*
,

Rate is independent of First order with

[B] . respect to B. Cannot confirm its
order of reaction with
Zero order with In 2 respect to B . (Another
t1 method is required.)
respect to B . 2 k

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4. Pseudo-order Reactions

For a reaction A + B + C + D -» products

where rate = k[A]m[B]n[C]°[D]P i

if B, C and D are used in large excess , the rate law becomes

rate = ki [ A]m where ki = k[B]n[C]°[D]p

The reaction is a pseudo mth order reaction .

5. Initial Rates Method

E . g . The acid catalysed hydrolysis of an ester is as follows :

HCI
CH3CO2C2H5 + H2O * CH3CO2H + C2H5OH
[ CH3C02C2H5]
0.25
r • ^ .

\ —*
x \
X \ ’ ! t
X X
x !
x v

0.2 -t ~t t • ? 1
t

*- —- --
4
-
j
- .• - •.. - L - —-
i>

0.15 i
X
X t
I X
i
X
V X
% X
I
'4

-
\
. ,..r
H-r \
v i
I * i- v |
~t
0.1 - \ X

x
x
M h-t-nrt- X

— Vi X

i [K Cl] = 1.0 mol dm'3

X

t r »\ X
i V --

» \ \
• r- ‘
X
r -xr?
x
t
l
0.05 \
- -f - »
hi -V -4-P ’,
—
X
1
x

i—H- —
:

h-M
V
x~~, r
I
4-4-14-
t " '
; x
X I *
X
Vx- f I 1.0 mol dm'3
TT1 -4-- 00 —- ——4- U
1 1
l V
\52 -
time
^
f* f

0 I i x
\

0 20 40 60 80 100' 120 140

Y
VS . V

32 32

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How to determine order of reaction of the reactant from a graph

Given a concentration-time graph, determine the order of reaction of the reactant on the
y-axis (i.e. CH3CO2C2H5) by:

Step 1: If graph is a decreasing linear graph, the order of reaction is zero.

Step 2: If graph is not linear, find at least two half-lives and prove that they are constant.
Hence, the reaction is first order with respect to that reactant.

Given a concentration-time graph, determine the order of reaction of the reactant which
has varying concentrations (i. e. HCI) by:

Step 1: Find the initial rates for both curves by drawing the tangent at time = 0 and
calculating the gradient of the tangent.

Step 2: Compare the change in initial rates to the change in concentration of that reactant
for each experiment, similar to that of the calculation/inspection method.

Collision Theory

For a reaction to occur , the reactant molecules must:

• Collide with a certain minimum energy (known as activation energy) and
• Collide with the correct orientation
Activation Energy
The activation energy, Ea is defined as the minimum energy which the colliding
molecules must possess before a collision will result in a reaction.

Factors Affecting Rate of Reaction and Rate Constant, k

1. Concentration of reactant

When the concentrations of reactants increase,

• The reactant particles are closer to one another
• The frequency of effective collisions increase, therefore rate of reaction increases
(Increasing the pressure for gaseous reactions will bring about the same effect.)

Note:
1. Changes in the concentrations of the reactants do not affect rate when:
• Reaction is zero order with respect to reactant
• Catalyst is already working at maximum capacity
2. Changes in the concentrations of the reactants do not affect rate constant , k .

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3. Catalyst

A catalyst provides an alternative mechanism/pathway with lower activation energy.

• This results in more particles with energy > Ea
• The frequency of effective collisions increases,
• Rate constant increases, hence rate of reaction increases
Note: A catalyst does not lower the activation energy of the reaction.

Number of
particles

Kinetic energy

Lined region represents no. of particles with energy > Ea

Gray shaded region represents no. of particles with energy > Ea
mm *cat
Maxwell-Boltzmann distribution curve showing the distribution of kinetic energies of
particles when the reaction is catalysed and uncatalysed.

Potential
energy /
kJ mot 1

EA E
^cat

reactants

AH
I products

Reaction coordinate
Energy profile diagram of catalysed and uncatalysed reaction .

Note: Rate constant, k , is only affected by catalysts and/or by a change in temperature .

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Reaction Mechanisms
To derive rate equations for a multi-step reaction:
Step 1: If the slowest step (i.e. rate determining step) is the first step, the rate equation
involves the reactants in the slowest step according to its stoichiometric ratio.

Step 2: If the slowest step is not the first step, write the rate equation involving the
compounds in the slowest step according to its stoichiometric ratio.

Step 3: The compounds which are not the reactant will have to be substituted by the
reactants by equating
Forward rate = Backward rate
then make the intermediate compound as the subject and substitute it to the rate equation
in Step 2. (Refer to lecture notes pg 35 & 36.)

Catalytic Mechanisms

1. Homogeneous catalysis
Reactants and catalyst are in the same phase.

E.g. Oxidation of I by S2O82' using Fe2+ catalyst

"

Step 1: S2082-(aq) + 2Fe2+(aq) -> 2S042 (aq) + 2Fe3+(aq) (Formation of Fe3+ intermediate)
"

Step 2: 2Fe3+(aq) + 2I (aq)'

2Fe2+(aq) + h(aq) (Regeneration of Fe2+ catalyst)

E. g. Oxidation of atmospheric SO2 by NO2

Step 1: S02(g) + N02(g) -» S03(g) + NO(g)

Step 2: NO(g) + 1/202(g) -* N02(g)

2. Heterogeneous catalysis
Reactants and catalyst are in different phases.

E.g. Haber process

N2(g) + 3H2(g) -* 2NH3(g) Catalyst: Fe(s)

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H2 Chemistry Remedial Worksheet

Topics: Chemical Equilibrium & Ksp

Chemical Equilibrium

• Dynamic equilibrium
o A reversible reaction is in dynamic equilibrium when
the rates of forward and backward reactions are equal, and
the concentrations of reactants and products remain constant

Concentration Rate
/ mol dm-3 * / mol dm-3 time-1

0.8 —
Forward
0.6 — HI rate

0.4

0.2 Backward
H2 = I2 rate
0 >
a time a time
Reaction at Reaction at
equilibrium equilibrium

• Position of equilibrium is the proportion of products to reactants in the equilibrium

mixture.
• Equilibrium constant,
o For a general reversible reaction:
aP + bQ cR + dS
^
there is a fixed relationship between the equilibrium concentrations of
reactants and products and it can be expressed as follows:
The power to which the reactants
and products are raised
[ R ]c [S ]d corresponds to the respective
Kc =
[ P ] a [Q ] b stoichiometric coefficients in the
equation of the reversible reaction.

where Kc is the equilibrium constant for the reaction in terms of

concentration.

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o For a reversible reaction involving gaseous reactants and products, the expression
for the equilibrium constant can also be expressed in terms of partial pressure.

For example
N204(g) 2N02(g)
p _ nNQ 2
Knp =
( PNO2 f ' N O2 x PT
PW. 204 nT

Note:
o They are constant at a given temperature. They are not affected by changes in
concentration, partial pressure or presence of catalyst.

o Kc and KP are not affected by temperature ONLY WHEN AH = 0.

o Kc expression does not include solids.

o Their values indicate the extent of a reaction, that is how far the reaction proceeds
[ products ]
to form products, since Kc =
[ reactants ]

If value of Kc is small (i.e. [products] < [reactants]), then position of

equilibrium lies to the left. Backward reaction is favoured more than the
forward reaction.
If the value of Kc is big (i.e. [products] > [reactants]), then position of
equilibrium lies to the right. Forward reaction is favoured more than the
backward reaction.

o Kc can be used for all reversible reactions but KP is only applicable to reactions
involving gaseous reactants and products.
o Kc =i-
‘ K
o For equilibria involving Heterogeneous systems
2-(aq)
• e.g. Co(H20)e2+(aq) + 4CI (aq) “

^ CoCL + 6H20(I)
[ CoCIA2 - ( aq ) ]
Kc =
[ CO( H20 )62+ ( aq ) ] [ Cr { aq )]4
[H20(l)] is not included as an aqueous system is present,
o For equilibria involving Homogeneous system
CH3C02H(l) + CH3CH2OH(l) CH3C 02CH2CH3(l) + H20(l)

Kc - [CH3C02C2H5 ( / )][H20( / )]
[ CH3C02 H ( I ) ] [CHZCH20H ( I ) ]
[H20(l) ] is included as a non-aqueous system is present.

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Factors affecting Chemical Equilibria

(i) Concentration
(ii) Pressure
(iii) Temperature
(iv) Catalyst

Le Chatelier’s Principle
o States that when a stress is applied to a reversible system at equilibrium, the
position of equilibrium will shift so as to minimise the stress.

For a given reversible reaction: aP + bQ ^ cR + dS

Stress factor Position of equilibrium Equilibrium constant

Increase in [P] or [Q] Right

No change
Increase in [R ] or [S] Left

lfa + b = c + d
No change
Increase in pressure
lfa + b > c + d
(only applicable for No change
Right
gaseous systems)
lfa + b < c + d
Left

If AH < 0 (exothermic)
Decrease
left
Increase in temperature
If AH > 0 (endothermic)
Increase
right

Addition of catalyst No change No change

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Calculations Involving Equilibrium Concentrations and Amounts

Heading reactants products

Initial

Change

Equilibrium

Step 1: Create the ICE table (I: Initial, C: Change, E: Equilibrium).

Step 2: The heading can be in concentration / amount / pressure.
Step 3: Fill in the known quantities from the question. (If there is unknown quantity, define
the term, e. g. let the initial amount of acid be x.
Step 4: Calculate the change in concentration/pressure/amount by using the mole ratio.
Step 5 : Calculate the equilibrium concentration/pressure/amount.
Step 6: Solve for the unknown, e.g. Kc.

Haber Process

3H2(g) + N2(g) AH = -92 kJ moF1

^ 2NH3(g)
The industrial conditions used are
- Temperature: 500 °C
- Pressure: 250 atm
- Catalyst: finely divided iron
Choice of conditions used
• Temperature (500 °C)
o By Le Chatelier’s Principle, a low temperature will cause the position of
equilibrium to shift right to favour the exothermic reaction. More ammonia will
be produced
o However at low temperatures, the rate of reaction is slow and it will take a
long time to reach equilibrium.
o Hence a combination of moderate temperature ( 500 °C) and a catalyst are
used to ensure that both yield and rate are high.

• Pressure (250 atm)

o By Le Chatelier ’s Principle, a high pressure will cause the position of
equilibrium to shift right to reduce the total amount of gases. More ammonia
will be produced.
o However reaction vessels that can withstand extremely high pressures will
involve a higher cost of production and maintenance.
o Hence an optimal pressure of 250 atm is used.

• Catalyst
o A catalyst of finely divided iron mixed with aluminium oxide as promoter is
used to increase the rate of reaction.
o Hence equilibrium can be achieved within a shorter time.

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Solubility product, Ksp

1 Solubility
• Solubility of a salt refers to the maximum amount that can dissolve in a solvent at a
given temperature to form a saturated solution.

• Units: mol dm-3 or g dm-3

• Solubility of a sparingly soluble salt depends on the presence of a common ion or

the formation of a complex ion .

(Recall: sparingly soluble salts are salts which dissolve to a small extent - what is known
as insoluble salts in ‘O’ Levels)

2 Saturated solution and solubility product

• A saturated solution is one in which the maximum concentration of ions has been
reached at a given temperature.

• The solubility product of a sparingly soluble salt is the product of the equilibrium
concentrations of the ions in a saturated solution, each raised to the power of its
coefficient in the equilibrium equation.
For example: AB2(s) ^ A2+(aq) + 2B (aq)

[O M* units: mol3 dm-9

o Ksp varies only with temperature

o To compare salts of same formula (producing the same number of ions

when dissolved) , Ksp values can be compared.

o Smaller the Ksp, the less soluble the salt

o To compare salts of different formula , solubility values should be

compared instead.

3 Converting between solubility and Ksp - 3 scenarios

(i) Calculate Ksp , given the solubility of salt

E.g. The solubility of lead(ll) iodide in water at 15 °C is 0.46 g dm-3.

Calculate its Ksp at this temperature.

[Pbh] = 0.46/461 = 0.001000 mol dm '3

Pbl2(s) Pb2+( aq) + 2I (aq) ~

0.001000 0.002000

Ksp = [Pb2+] [I-]2

= (0.001000) (0.002000) 2
_
= 4.00 * 10 9 mol3 dm-9

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(ii) Calculate solubility of salt in water, given Ksp

_5
E. g. Given that the Ksp of calcium hydroxide is 3.20 * 10 mol3 dm-9 , calculate its solubility
in water.

Let the solubility of calcium hydroxide be x

Ca(OH) 2(s) ^ Ca2+(aq) + 20H-(aq)
x 2x

Ksp = [Ca2+] [OH- ]2

3.20 x 10-5 = x (2 x)2
4x3 = 3.20 x 10-5
x = 0.0200 mol dm-3

(iii) Calculate solubility of salt or Ksp where common ions are present

E.g. Given the Ksp of lead(ll) iodide is 4.0 x 10-9 mol3 dm-9, calculate the solubility of
lead(ll) iodide in a solution of 0.10 mol dm 3 of potassium iodide.
~

Let the solubility of lead(ll) iodide in potassium iodide be x.

Pbl2(s) Pb2+(aq) + 2I-(aq)
^ x 2x (from lead(ll) iodide) + 0.10 (from KI)
2 + - 2
Ksp = [Pb ] [I ]
= (x) ( 2 X + 0.10) 2
Since x « 0.10,
4.0 x 10 9“

= (x) (0.10) 2
x , = 4.00 x 10 7 mol dm-3
“

‘Compare this value with the solubility of lead(ll) iodide in water. Solubility of lead(ll)
iodide decreases in KI due to the presence of common ion, I-.

Factors affecting solubility

• Solubility of a sparingly soluble salt can be decreased due to the presence of a
common ion from a second source.

Pbl2(s) ^ Pb2+(aq) + 2I (aq) “

(D
KI(aq) -> K+(aq) + I-(aq) (2 )

By Le Chatelier’s Principle, the presence of the common ion , I- causes the position
of equilibrium of (1) to shift left to reduce the concentration of I-.

• Solubility of a sparingly soluble salt can be increased by the formation of a soluble

complex

AgCI(s) Ag+(aq) + C|-(aq) (1)

^
Ag+ ( aq) + NHs(aq) [Ag(NH3) 2]+ (2)
^
[ Ag+] decreases due to the formation of complex ion, [Ag(NH3) 2 ]+.
By Le Chatelier’s Principle, the position of equilibrium (1) shifts right to increase the
concentration of Ag+.
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Precipitation of sparingly soluble salts

To solve questions on prediction of precipitation

Step 1: Identify the precipitate to be formed and calculate the concentration of each ion.
amount of ion
[ion] =
total volume of mixture
*When there is equal volume of solutions mixed, the concentration of each ion is halved .
Step 2: Find the ionic product.
Step 3: If Ionic product > Ksp , precipitate is formed.
If Ionic product = Ksp , no precipitate is formed. Solution is saturated.
If Ionic product < Ksp , no precipitate is formed. Solution is unsaturated.

Selective precipitation
• An ion can be separated from another ion by selective precipitation due to the
difference in solubility or Ksp of the sparingly soluble salt.
• For salts with same formula, we can compare the Ksp value directly. The smaller
the Ksp , the less soluble the salt.
• For salts with different formula, we need to calculate the solubility of the salts to
determine which salt is less or more soluble.

E. g. Solid NaOH is slowly added to a solution containing 0.010 mol drrr3 Mg2+ and
0.010 mol dm-3 Fe2+.

Kspl mol3 dm-9 Mg(OH) 2: 1.2 x 10 11

~
Fe(OH) 2: 1.6 x 10
“ 14

Calculate the pH at which the maximum amount of Fe2+ that can be extracted from the
solution. Hence, calculate the concentration of Fe2+ remaining in the solution.

Since both sparingly soluble salts are of same formula, we are able to compare the Ksp
directly to determine which is less or more soluble. Since Ksp of Fe(OH)2 is lower, Fe(OH)2
is less soluble and will be formed first.

We need to determine:

• The concentration of OH- needed to precipitate nearly all of the Fe2+, where nearly
all of Mg2+ is in solution.
• This occurs when ionic product of Mg(OH) 2 is less than its solubility product.

• [Mg2+] [OH12 < Ksp of Mg(OH) 2, [O H ] <

[ Mg ' ]
1

• With this [OH-], we are able to find the [Fe2+] that exists in equilibrium with OH , i.e. “

[Fe2+] that is not precipitated out, by equating

[Fe2+] [OH-]2 = KsP of Fe(OH) 2 [Fe ] 2+

=
[ OH'

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H2 Chemistry Remedial Worksheet

Topic: Ionic Equilibria

Acids and Bases

According to Bronsted-Lowry Theory, An acid is a proton donor (H+ donor)

A base is a proton acceptor (H+ acceptor)

Basicity of an acid refers to the number of protons per molecule that can be donated
in a reaction

Acidity of a base refers to the number of protons per molecule that can be accepted
in a reaction

A conjugate acid-base pairs:

conjugate acid-base pair

f
HA + B *
A
’
+ BH+
acid base conj. base conj. acid of
of HA B
4 4
conjugate acid-base pair
The relative strength of acid and bases depends on whether it dissociates completely or
partially in water.

• For a strong acid , it has a greater tendency to donate proton. Its conjugate
base is weak and has negligible tendency to accept a proton.

For example, HCI + H 2O -» Cl "

+ H30+

• For a weak acid , it has a negligible tendency to donate proton . Its conjugate
base is strong and has a great tendency to accept a proton.

For example, CH3COOH + H 2O CH3COO "

+ H30+
^
Acid-Base Equilibria

For a weak monoprotic acid HA: For a weak monoacidic base B:

HA(aq) + H2OO) ^ H30+(aq) + A (aq) "
B(aq) + H20(l) BH+(aq) + OH (aq)
^
"

[H3Q+ ][A- ] [BH* ][QH~ ]

Ka = [HA]
units: mol dm-3 Kb = units: mol dm " 3
[ B]

pKa = - lg Ka (no units) pKb = - lg Kb (no units)

Ka is a constant at constant temperature Kb is a constant at constant temperature

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Ionic product of water

Water undergoes self-ionisation: H20 (l) + H20(l) HsO+(aq) + OH (aq )

'

Kw = [H30+] [OH ] units: mol2 dm-6

pKw = -lg Kw (no units)
Kw is a constant at constant temperature

mol2 dm-6

^
14
Kw = 1.0 x 10 '

only at 25 °C
pKw = 14.0

Important formula: Kw = Ka x Kb

pH of Solution

pH is defined as the negative of the logarithm to base 10 of the hydrogen ion

concentration in mol dm-3

pH = - lg [H30+]

Important formulae: pOH = - lg [OH"] pH + pOH = 14.0

Strong acids and bases Weak acids and bases

For strong acid: HA + H20 -» HsCT + A "

For weak acid: HA + H20 HsO+ + A"
[HsO+] = [HA] [H30+] = VKax [HA]initia|

For strong base: BOH -» B+ + OH- For weak base: B + H20 ^ BH+ + OH-
[OH- ] = [BOH] [OH- ] = VJVtBjinitial

pH of pure water

Water undergoes self-ionisation:

H20(l) + H20(l) ^ HsO+(aq) + OH-(aq) AH9 = +58 kJ mol- 1

When temperature increase, according to Le Chatelier ’s Principle, position of equilibrium

shifts to the right, favouring the forward endothermic reaction to remove some of the
added heat.

[H30+] and [OH ] increase to the same extent but [H30+ ] = [OH- ]. Water is still neutral .

Kw increase with temperature. [pH of water = 7.0 (only at 25 °C) ]

Note: Must know that self-ionisation of water is an endothermic reaction.

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Salt Hydrolysis

Salt of a Strong Acid + Strong Base Salt of a Weak Acid + Weak Base
(NEUTRAL) (DEPENDS)

HCI + NaOH NaCI + H2O CH3CO2H + NHs CH3CO2NH4

lonization of salt: NaCI + aq -» Na+ + Cl ”

Ionisation of salt:
CH3CO2NH4 -> CH3CO2- + NH4+

The Na+ has low charge density , thus does In this case, it depends on the acid-base
not hydrolyse in water. strength of the ions:
-^
• If Ka > Kb salt solution is acidic
Cl is a weak conjugate base of strong acid
”
--
• If Ka = Kb >salt solution is neutral
HCI, thus does not hydrolyse in water. • If Ka < Kb > salt solution is basic
No salt hydrolysis

Salt of a Strong Acid + Weak Base Salt of a Weak Acid + Strong Base
( ACIDIC) (Basic)

HCI + NH3 NH4CI CH3CO2H + NaOH CH3C 02Na

Ionisation of salt: NH4CI NH4+ + cr lonisation of salt:

CH3C02Na CH3C02 + Na+
"

NH4+ is a conjugate acid of a weak base, it CH3CO2 is a conjugate base of a weak

can hydrolyse in water. acid , it can hydrolyse in water.

NH4+ + H2O + CH3CO2- + H2O -

^ NH3 + H30 ^ CH3CO2H + OH
Cl is a weak conjugate base of strong acid The Na+ has low charge density, thus does
'

HCI, thus does not hydrolyse in water. not hydrolyse in water.

Salt solution is acidic Salt solution is basic

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Buffer

Buffer is a solution that can resist large pH changes when small amount of acid or
base is added.

Acidic Buffer Alkaline Buffer

An acidic buffer is made up of a weak acid An alkaline buffer is made up of a weak

and conjugate base of the weak acid. base and conjugate acid of the weak
base .

Example (Ethanoic Acid + Sodium Ethanoate) Example (Ammonia + Ammonium Chloride)

CH3COOH + H2O ^ CHsCOO- + H3O+ NH3 + H2O NH4+ + OH-

CH3C02Na -» CHsCOO + Na+ *
^
NH4CI NH4+ + cr

When small amount of acid is added, When small amount of acid is added
CHsCOO- + H30+ -» CH3COOH + H20 NH3 + H30+ -> NH4+ + H2O

The excess H30+ reacts with CH3COO- that The excess H30+ reacts with NH3.
comes mainly from the dissociation of the Thus, [H30+] remain almost constant.
salt. Thus, [HsO+ ] remain almost constant. The pH remain almost constant.
The pH remain almost constant.
When small amount of alkaline is added
When small amount of alkaline is added , NH4+ + OH NH3 + H20
"

CH3COOH + OH -» CHsCOO + H20

' '

The excess OH reacts with NH4+ that

"

The excess OH reacts with CH3COOH. comes mainly from the dissociation of the
"

Thus, [OH-] remain almost constant. The salt. Thus, [OH-] remain almost constant.
pH remain almost constant. The pH remain almost constant.
[Salt] [Salt]
pH = pKa + lg [Acid] pOH = pKb + lg [Base]

Note: When writing the equations when a small amount of acid/alkali is added to the
buffer system, a full arrow ( -») must be used.

Maximum Buffering Capacity

It is the pH at which the buffer solution is able to resist pH changes at its maximum
capacity.

For an acidic buffer , [acid] = [salt] pH = pKa

For an alkaline buffer , [base] = [salt] pOH = pKb

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Titration Curves

Indicator Acid colour Alkaline colour pH range

Methyl orange red yellow 3.1 - 4.4
Thymolphthalein colourless Blue 9.4 - 10.6

Titration Marked pH Change Choice of Indicator

Methyl Orange
Strong Acid - Strong Base 3 - 11
Thymolphthalein
Weak Acid - Weak Base None No suitable indicator
Strong Acid - Weak Base 3-7 Methyl Orange
Weak Acid - Strong Base 7 - 11 Thymolphthalein

(a ) Strong Acid - Strong Base (e.g. HCI titrated with NaOH)

• Before titration, HCI is a strong acid, [H30+] = [HCI]

pH = - Ig [H30+]

• Equivalence point is pH 7 as the salt formed does not undergo hydrolysis.

Suitable indicator is thymolphthalein or methyl orange .

• After equivalence point , there is an excess of NaOH. pH of solution depends on the

amount of excess NaOH added.
[OH-] =
Amount of excess NaOH _
(VNaOH added VNaOH equivalence point ) * NaOH
'
^
* pOH = -Ig [OH ]
Total volume of solution
-
vNaOH added + vHCI

* pH = 14 - pOH
(b) Weak Acid - Strong Base (E.g. CH3COOH titrated with NaOH)

• Before titration, CH3COOH is a weak acid , [H30+] = jKa* [CH3 COOH]

pH = - Ig [HsO+]

[Salt]
• Before the equivalence point, there is an acidic buffer, pH = pKa + Ig
[Acid]

• When half neutralised, it is the maximum buffering capacity, pH = pKa

• At equivalence point, the salt formed undergoes salt hydrolysis and pH > 7.
Suitable indicator is thymolphthalein .
Salt hydrolysis equation: CH3COO- + H2O CH3COOH + OH-
^
l
[OH-] = JKb x [CH3 COO - ] =
pOH = -Ig [OH-]
pH = 1 4 - p O H
^ x [CH 3 COO - ]

• After equivalence point , there is an excess of NaOH. pH of solution depends on the

amount of excess NaOH added.
[OH-] =
Amount of excess NaOH _ (VNaOH added VNaOH at equivalence point ) x ^NaOH
~

* pOH = -Ig [OH ]

Total volume of solution
-
vNaOH added + VCH3 COOH

pH = 1 4 - p O H
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(c) Strong Acid - Weak Base (E.g. NH3 titrated with HCI )

• Before titration, NH3 is a weak base, [OH- ] = JKb * [NH3 ]

pOH = - Ig [OH-]
pH = 14 - pOH
[Salt]
• Before the equivalence point, there is an basic buffer, pOH = pKb + Ig [Base]

• When half neutralised, it is the maximum buffering capacity, pOH = pKb

• At equivalence point , the salt formed undergoes salt hydrolysis and pH < 7.
Suitable indicator is methyl orange .
Salt hydrolysis equation: NH4+ + H2O ^ NH3 + H30+

* [pHH30= -] ig= JK [NHj] = ITT * [NH ]

+ X
4
3 Kb
[H30 + ]
*
• After equivalence point, there is an excess of HCI. pH of solution depends on the
amount of excess HCI added.
_
[H3 o+ ] = Total volume of solution VHCI added ^
Amount of excess HCI ( '
HCI at equivalence point ) x C|-( CI

* pH = -ig [H3 O + ]
VHCI added+ VNH3

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H2 Chemistry Remedial Worksheet

Topic: Electrochemistry
( A ) Electrochemical Cell (spontaneous redox reactions)
.
Standard Electrode Potential Ee. and Standard Cell Potential, £®ceii

The standard electrode (redox) potential , E® , of a half-cell is the maximum potential

difference between the electrode potentials of the half-cell and hydrogen electrode (taken
to be 0.00 V) measured under standard conditions.

The standard cell potential, E®ceii, is the maximum potential difference between two
electrodes of a galvanic cell measured under standard conditions .

Units for both E® and E®ceii: Volt (V)

Measuring Standard Electrode Potentials

1. Metals in contact with their ions in aqueous solution

Example A Determination of E®(Zn2+/Zn)

high resistance voltmeter
electron flow
255C
V
zinc
(-) salt bridge <- H2(g)
at 1 bar and 25 °C

1 mol dm-3
Zn2+( aq) m platinised Pt
Si-

—
'

% (+)
-
Ham

1 mol dm-3
H+(aq)

2. Non-metals in contact with their ions in aqueous solution

Example B Determination of E®(Cl2/CI ) "

high resistance voltmeter

electron flow 25SC

Ch(g)
—
0 H2( g)

w
at 1 bar and 25 °C salt bridge
at 1 bar and 25 °C

Pt
(+) platinised R

1 mol dm-3 mr 0
° SB o
°
(- )
1 mol dm-3
Cl-( aq) \ H+( aq)

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3. Ions of the same element in different oxidation states

Example C Determination of E® (Fe37Fe2+)

high resistance voltmeter

electron flow

Pt
0
salt bridge
H2(g)
25°C

at 1 bar and 25 °C

1 mol dm-3
Fe2+( aq)
and
1 mol dm-3
Fe3+(aq)
s
m
*
\ platinised Pt
(- >
1 mol dm-3
H+( aq)

Note:
Standard conditions:
• Temperature of 298 K or 25 °C
• Partial pressure of any gas involved at 1 bar (105
-3
Pa)
• Concentration of any ions involved at 1 mol dm
Electron flows from the anode (-) to the cathode (+).

Comparing E values
°
The more positive the value of E® , the more reduction is favoured .
(i.e. stronger oxidising agent)

The more negative the value of E®, the more oxidation is favoured .
(i. e. stronger reducing agent)

Cell Diagram for Electrochemical Cell

‘Electrode | Reduced form | oxidised form || oxidised form | reduced form | ‘Electrode

Anode (- ) I Cathode (+)

Salt Bridge

‘Only include the electrode (inert) if it is not the reduced form.

E.g. Write the cell notation for the electrochemical cells from Example A , B and C .

Example A : Zn(s) | Zn2+(aq) || H+(aq) | H2(g) | Pt(s)

Example B : Pt(s) | H2(g) | H+(aq) || Cl2(g) | Cl (aq) | Pt(s)

"

Example C : Pt(s) | H2(g) | H+(aq) || Fe3+(aq) , Fe2+(aq) | Pt(s)

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Calculating E®ceii

E ° ceii = E°(reduction) - Ee(oxidation)

the Feasibility of Reaction

Predicting
When Eeceii is positive , reaction is spontaneous (feasible) .

When E°ceii is negative , reaction is non-spontaneous (but the reverse reaction is

spontaneous).

Note: When E®ceii is zero or near zero, reaction is at equilibrium or reaches equilibrium
soon.

Limitations of predictions: E°ceii > 0 but reaction does not take place because:
(i) Slow rate of reaction due to high activation energy .
(ii) Reaction is carried out at non-standard conditions.

Effect of Concentration on E®
For the general equation, Mn+(aq) + ne ^ M(s)

If [Mn+(aq) ] increases ,
• position of equilibrium shifts to the right (i.e. reduction favoured)
• E°(Mn7M) becomes more positive.
(B) Electrolytic Cell (non-spontaneous redox reactions)
electron flow
HiF

** •

-
electrolyte '

I
I1
....

Selective Discharge of Ions

1. Position of ion in the electrochemical series
• Cations are reduced at the ®cathode
Cation with most positive E is preferentially reduced

• Anions are oxidised at the anode

®
Anion with most negative E is preferentially oxidized

Electrolysis of Ageuous Solutions

For electrolytes which are aqueous , water may be oxidised or reduced .

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Concentration of Ions
Ions that are present in high concentration may be preferentially discharged , even
though its position in the electrochemical series makes it unfavourable.

Nature of Electrodes
An active electrode (particularly the anode) can participate in the oxidation process.

Stoichiometry of Electrolysis

Q = It
where Q = quantity of charge Units: Coulomb (C)
I = current Units: Ampere (A)
t = time Units: second (s)

Charge carried by 1 mole of electrons = 1.602 x 10 19 x 6.02 x 1023 = 96500 C mor 1

“

(96500 C mol-1 = 1 F , where F is Faraday. Also known as Faraday constant.)

Q = neF
where ne = amount of electrons

F = Le
where F = Faraday constant
L = Avogadro constant
e = charge on one electron

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Comparison between Electrochemical Cell and Electrolytic Cell

Electrochemical cell Electrolytic cell

electron flow electron flow

V +

anode salt bridge cathode anode cathode

(-) (+ > (+) (-)
i

Oxidation half cell Reduction half cell

More More Anion with Cation with
negative E ®
positive E®
most most
undergoes undergoes negative E° positive E° is
oxidation reduction is preferentially
preferentially reduced
oxidised

Similarities:

Anode Cathode
electron flow
Oxidation Reduction

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