1

Sem 1 Chapter review (answer)

Atom, molecule and ions
Deflection of elementary particles in electrical field and magnetic field
a. Identify which species below which give
pathway I and II:
Electron, neutron, 1H+, 2D+
I: 1H+, II: 2D+
b. Compare the angle of deflection between
pathway I and II.
∠ of I is double of ∠ of II
c. Which specie deflect further? Why?
II. It is heavier

Relative atomic/molecular/formula mass

Find abundance from relative atomic mass.
1. The relative atomic mass of X is 79.99. Calculate the percentage abundance of the isotopes 79X and 81X.
Assume % of 79X = a, % of 81X = 100-a
79𝑎+(100−𝑎)81
100
= 79.99

𝑎 = 50.5
% of 79X = 50.5 and % of 81X = 100-50.5 = 49.5
Find relative mass from abundance.
2. Boron exists naturally as boron-10 and boron-11 with their relative abundance of 18.7% and 81.3%,
respectively, while fluorine exists naturally as only fluorine-19. Calculate the relative molecular mass of
boron trifluoride.
18.7𝑥10+81.3𝑥11
S1: find Ar of boron = = 10.8
100
S2: find Mr of BF3 = 10.81 + 3(19) = 67.8

Mass spectrum & relative mass

Find relative mass from spectrum.
1. The mass spectrum of element X is shown below.

Determine the relative atomic mass of X.

100𝑥64+56𝑥66+8𝑥76+38𝑥68 13288
Ar for X = 100+56+8+38
= 202
= 65.78
 2

Identify fragment ions and molecular ions

2. The mass spectrum of ammonia is show below.

Identify the ions which cause the peaks at m/e = 16 and m/e =18.
Since Mr for NH3 is 17 (14 + 3x1), m/e 16 is due to fragment ion NH2+ (14 + 2x1), m/e 18 is due to
molecular ion of NH3 with hydrogen-2 isotope (14 + 2x1 + 1x2)

Stoichiometry
Write balance equation, calculation involving mole ratio of two equations, calculation for % of yield
1. State the mole ratio between CH3CH3 and (CH3CH2)4Pb.
CH3CH3 + Cl2 → CH3CH2Cl + HCl
4CH3CH2Cl + 4NaPb → (CH3CH2)4Pb + 3Pb + 4NaCl
By inspection:
4CH3CH3 ≡ 4HCl ≡ 4CH3CH2Cl ≡ (CH3CH2)4Pb
Ratio of Cl2: CH3CH2Cl = 4:4 = 1:1
Ratio of Cl2: (CH3CH2)4Pb = 4:1
Ratio of HCl: (CH3CH2)4Pb = 4:1
Ratio of CH3CH3: (CH3CH2)4Pb = 4:1

2. Pure titanium is obtained commercially in a two-stage process starting from rutile, TiO2. Rutile is reacted
with chlorine gas and coke to yield liquid titanium(IV) chloride, TiCl4, which is then reduced by magnesium.
Write the equations for the reactions involved.
TiO2 + C + 2Cl2 → TiCl4 + CO2
TiCl4 + 2Mg → Ti + 2MgCl2

3. Urea, (NH2)2CO, is a chemical fertilizer which decomposes into carbon dioxide and ammonia gas in the
presence of water. State number of moles of gas molecule formed from 1 mole of urea.
(NH2)2CO + H2O → CO2 + 2NH3
1 mol CO2 + 2 mol NH3 = 3 moles of gas

4. A volume of 10 cm3 C2H6 has burned completely in 50 cm3 O2.

a. Write equation for this reaction.
7
C2H6 + 2O2 → 2CO2 + 3H2O
b. Which compound is excess reagent? Limited reagent?
Excess reagent = O2, limited reagent = C2H6
c. What is the volume of CO2 formed?
From equation, 1 mol C2H6 formed 1 mol CO2
From experiment, 10 cm3 C2H6 formed 30 cm3 CO2
 3

5. Cl2 was used to react with excess iron to produce iron(III) chloride, FeCl3. If the percentage of the actual
yield of FeCl3 obtained in the laboratory is 82.0%, calculate the mass of FeCl3 produced. Given theoretical
yield of FeCl3 is 498 g.
Mass of FeCl3 produced = 498 x 82.0% = 408g

Electronic structure: Draw energy level diagram, identify electron transition, calculate wavelength, f, energy, IE
1. The energy-level diagram for a hydrogen atom shows several electronic transitions with frequencies f1, f2, f3,
f4, and f5.

a. Identify electronic transitions with produce Lyman series and Balmer series.
Lyman: f1 to f3
Balmer: f4 to f5
b. Draw emission spectrum for Lyman and Balmer series. Label the lines in the spectrum for each
electronic transitions.

f1 f2 f3 f4 f5

c. Which line is used to calculate ionisation energy of hydrogen? f3

d. Which line produces highest frequency and lowest wave length? f3

2. P, Q and R, are elements.

[Proton number P = 20, Q = 24, R = 29]
a. Fill in the blanks for electronic configuration of P, Q and R.
Element Electronic configuration Position in the Periodic Table
Group/Period
P 1s22s22p63s23p64s2 Group 2/s-block, period 4
Q 1s22s22p63s23p63d54s1 d-block, period 4
R 1s22s22p63s23p63d94s2 d-block, period 4
b. Write box-arrow notation electronic configuration of Q3+

Q3+: 1s22s22p63s23p63d3

↿⇂ ↿⇂ ↿⇂↿⇂↿⇂ ↿⇂ ↿⇂↿⇂↿⇂ ↿ ↿ ↿

c. Identify number of unpaired electron in Q3+. Three

d. Write valence electronic configuration of R+. 1s22s22p63s23p63d94s1

e. State the principal quantum number of the removed electrons from R to form R+. 4

f. Write valence electronic configuration of atom P. 4s2

g. How many valence electrons in atom P. Two

h. How many orbitals of atom P are fully filled? Ten

 4

i. Identify element which is isoelectronic with ion P. Q

3. The number of electrons occupying the different orbitals of atom L are shown in the following table.
Orbital Number of electrons
s 7
p 12
d 5
Write the electronic configuration of L,
1s22s22p63s23p63d54s1

Chemical bonding
Molecular geometry: draw Lewis structure, predict molecular shape, state bonding pair, lone pair, bond angle
Fill in the blanks for the name of the shape of molecules:
Bent/ V-shape See-saw Trigonal planar
Linear Square planar Trigonal bi-pyramidal
Octahedral Tetrahedral Trigonal pyramidal
Square pyramid T-shape

No. of bonding
pair 2 3 4 5 6
No. of lone
pair
None Linear Trigonal planar Tetrahedral Trigonal bi- Octahedral
pyramidal
1 Bent/V- Trigonal See-saw Square pyramid
shape pyramidal
2 Bent/v- T-shaped Square planar
shape
3 linear T-shaped

Identify the molecular geometries for the following species:

1. SF6 2. SF4 3. I3- 4. [Fe(CN)6]3- 5. PO43- 6. PH3
Octahedral seesaw linear Octahedral tetrahedral Trigonal
pyramidal
7. ClO4- 8. O3 9. ClF2+ 10. SO2 11. SO3 12. SO32-
tetrahedral Bent/v- Bent/v- Bent/v- Trigonal Trigonal
shaped shaped shaped planar pyramidal

Fill in the blanks to compare the properties of methane, ammonia and water
Compound Methane Ammonia Water
Lewis
structure

Number of Bp – 4 Bp – 3 Bp – 2
bonding pair Lp - no Lp - 1 Lp - 2
and lone pair

Molecular Tetrahedral Trigonal pyramidal Bent/V-shaped

geometry
 5

Bond angle 109.5o 107o 104o

Type of sp3 sp3 sp3
hybridisation

Diagram of
overlapping
of orbitals

Polarity Non-polar molecule Polar molecule Polar molecule

Types of Van der Waals forces Hydrogen bond Hydrogen bond

intermolecula
r forces
Solubility in Insoluble Soluble -
water

Electrical Insulator Electrolyte Electrolyte

conductivity

Acidity and Neutral Basic Amphoteric

basicity

Fill in the blanks to compare the shape of CH3-, CH3+ and ·CH3
Compound CH3- CH3+ ·CH3

Lewis structure

Number of bonding pair Bp- 3 Bp- 3 Bp- 3

and lone pair Lp- 1 Lp- no Lp- no
*contain single
electron

Molecular geometry Trigonal pyramidal Trigonal planar Trigonal pyramidal

Bond angle 109.5o<x<90o 120o 109.5o<x<90o

Type of hybridisation sp3 sp2 sp2

 6

Oxo-anion Nitrate Sulphate Carbonate

Lewis
structure

Number of Bp- 3 Bp- 4 Bp- 3

bonding pair
and lone pair
Molecular Trigonal planar Tetrahedral Trigonal planar
geometry

Bond angle 120o 109.5o 120o

Type of sp2 sp3 sp2

hybridisation

Number of Sigma- 3 Sigma- 4 Sigma- 3

sigma bond Pi- 1 Pi- 2 Pi- 1
and pi bond

Functional Lewis structure/ type of Polarity Intermolecular Acidic/basic/neutral

group hybridisation for C atom forces

Ethyne None polar Van der Waals neutral

forces

sp

polar Van der Waals neutral

Chloroethane forces

sp3

Ethanol polar Hydrogen bonding Weak acid

sp3
 7

polar Van der Waals neutral

forces
Ethanal

sp2

Ethanoic acid polar Hydrogen bond Weak acid

sp2

Ethanamine
polar Hydrogen bond Weak base

sp3

Ethanamide polar Hydrogen bond neutral

sp2
State the bond angle for the following compound

∠𝑎= 104o, ∠𝑏= 109.5o, ∠𝑐= 120o, ∠d= 107o

Ionic and covalent compound

1. Classify the following compounds into ionic and covalent compound
HCl, BeCl2, AlBr3, C6H5NH3Br, NaBr, MgCl2, AlF3, KI
Ionic Covalent
AlBr3, C6H5NH3Br, NaBr, MgCl2, AlF3, KI BeCl2, HCl, C6H5NH3Br

a. Which of the ionic compound having strongest ionic bond? AlF3

b. Which of the compound has both ionic and covalent bond? C6H5NH3Br
 8

2. Identify the following species with dative/co-ordinate bond

Al2Cl6, NH4+, [Fe(CN)6]3-, CO, BeCl2, PH4+
Dative bond/co-ordinate bond Without dative/co-ordinate bond

Al2Cl6, NH4+, [Fe(CN)6]3-, CO, PH4+ BeCl2

Which of the compound/ion has most number of co-ordinate/dative bond? [Fe(CN)6]3-

Which of the compound/ion has strongest covalent bond? CO (consist triple bond)

3. Identify the position of periodic table for the following element and state types of bonding/intermolecular
forces present
Element V W X Y Z
Atomic number 3 8 13 16 26
Valence electronic 2s1 2s22p4 3s23p1 3s23p4 3d64s2
configuration
Period 2 2 3 3 4
Group 1 16 13 16 Group 8 (d-
block)
Types of Metallic Van der Metallic Van der Metallic
bonding/intermolecular Waals Waals
forces
Which of the following elements has strongest metallic bond?
Z(It consists of most number of valence electrons, strongest metallic bond)

State of matter:
A. Gas
Gas Law Boyle law Charles law Avogadro law
Formula P1V1 = P2V2 𝑉1 𝑉2
= V = kn
𝑇1 𝑇2

Graph P vs V V vs T
1
P vs
𝑉

*Sketch line/curve at P1 and P2 where

P2>P1

*Sketch line/curve at T1 and T2 where

T2>T1
 9

Ideal gas vs non-ideal gas

Ideal gas Non-ideal gas
Assumption of ideal behaviour: Factors which cause non-ideal behaviour:
• Intermolecular forces? • Intermolecular forces exist between particles
No intermolecular forces between particles • Gas particles have volume
• Volume of gas? • Polar molecules
Gas particles have no volume/negligible Conditions to approach ideal gas:
volume
• Low pressure
• High temperature

State types of deviation for gas L and M before p = x

atm.
L: negative deviation
M: positive deviation
Explain why gas L show deviation before p = x.
L is polar molecule, has greater intermolecular forces
Which of the gas L or M is H2? Why?
M. H2 gas is small molecule and non-polar. It behave
almost like ideal gas

Ideal gas equation

Formula Example
PV = nRT Gas X of mass 0.118 g was filled into a 250 cm3 flask at 298 K and 73.5 kPa. What is the mass
of 1 mol of the gas? [Universal gas constant is 8.31 J K-1 mol-1]
Express in term of 𝑚𝑅𝑇
Mr = 𝑃𝑉
density: 0.118𝑥8.31𝑥298
𝑀𝑟 𝑃 Mr = 73.5𝑥103 𝑥250𝑥10−6 = 15.9
𝜌= 𝑅𝑇

One mole of any gas occupies the same volume under the same temperature and
pressure. Calculate the volume of one mole of gas at standard temperature and
pressure.
At STP, T = 0oC = 298K, P = 1 atm = 101kPa = 101x103Pa
Express in term of 𝑛𝑅𝑇
molar mass: V= 𝑃
𝑚𝑅𝑇 1𝑥8.31𝑥298
Mr = 𝑃𝑉 V= 101𝑥103 = 0.0245m3 = 24.5 dm3
 10

PV P'V' A sample of oxygen gas has a volume of 1.2 x 10-3 dm3 at a temperature of 2.0oC and
=
T T'
pressure of 2.4 atm. What is the volume of the sample of gas under room condition?
Room condition, T = 25oC, P = 1.0 atm
V1 = 1.2x10-3, T1 = 2.0oC, P1 = 2.4 atm
V2 = ?, T2 = 25oC, P2 = 1.0 atm
𝑃1 𝑉1 𝑇2 2.4𝑥1.2𝑥10−3 𝑥25
V2 = x
𝑇1 𝑃2
= 2.0𝑥1.0
= 0.036 dm3 = 3.5x10-2 dm3
Dalton’s law

1. Define in words: Dalton’s law state that the total pressure of a mixture of gases equals the sum of the
partial pressures of the gases present in the mixture

2. Define in formula: Ptotal = PA + PB + PC + …, where PA, PB, PC are the partial pressures of gases A, B and C
respetively

Example: Apply Boyle’s law and Dalton’s law

Calculate total pressure when the stopcock is opened

For N2, P1V1=P2Vtotal

200x6=P2(6+4),
P2=120kPa

For H2, P1V1=P2Vtotal

500x4=P2(6+4),
P2=200kPa

Phase diagram: sketch phase diagram for water and COP2total = 120+200 = 320kPa
a. Carbon dioxide is a gas at 25.0 °C and 1.00 atm. Its triple point is at -56.4 °C and 5.11 atm, and its
critical point is at 31.1 °C and 73.0 atm.
Sketch and label the phase diagram for carbon dioxide. [3]

b. The table below lists the temperature and pressure for the critical point and the triple point of a substance X.
Temperature/oC Pressure/atm
Critical point 31 73
Triple point -57 5
X sublimes at -78 oC under atmospheric pressure. The freezing point of X increases by 2oC for every increase
of 10 atm in pressure.
Based on the information given above, sketch the phase diagram of X. [4]
 11

Apply kinetics theory to explain changes of physical states

Changes in kinetic Changes in the Changes in the
Process energy of particles movement of particles distance/arrangement of
particles
Change from move Change from random
Boiling increase freely and colliding arrangement to far apart
each other to moving
randomly in all
directions
Change from vibrate Change from close
Melting increase about in their position together in regular
to move freely and pattern to random
colliding each other arrangement
Change from moving Change from far apart to
Condensation decrease randomly to move random arrangement
freely and colliding
each other
Change from move Change from random
Freezing decrease freely and colliding arrangement to close
each other to vibrate together in regular
about in their position pattern
Change from vibrate Change from close
Sublimation decrease about in their position together to far apart
to moving randomly
in all directions

Solid
Draw unit cell for NaCl (simple cubic) and I2, CO2 (face centered cubic)
 12

Kinetics
1. Deduce order of reaction from graph/ plot graph to deduce order of reaction
a. The reaction: W + X → Y + Z was conducted at two different temperatures and the results are shown in
the graphs below.

What is the rate equation for the above reaction?

First order with respect to X, zero order with respect to W

b. The graphs of initial rate versus concentration of reactants for the reaction X + Y → Z are shown below.

What is the order of the reaction with respect to X and Y?

First order with respect to X, second order with respect to Y

2. Deduce order of reaction from initial rate data

The kinetic data for the reaction A + 2B → C at a certain temperature is shown in the following table.

Experiment Initial Initial rate of What is the rate of the reaction?

concentration reaction Zero order with respect to B, second order with
[A]o [B]o respect to A
1 a b r
2 2a b 4r
3 a 2b r

3. Deduce order of reaction from rate constant.

Cyclopropane decomposes into propene through the ring opening of cyclopropane according to the
equation: C3H6(g) → CH2=CHCH3(g)
The rate constant for the decomposition is 15.12 s-1 at 400oC.
Write the rate equation for the decomposition of cyclopropane.
Since unit for rate constant is s-1, it is first order with respect to C3H6.
Rate = k[C3H6]
 13

4. Calculate half-life from rate constant.

The rate constant for the decomposition is 15.12 s-1 at 400oC.
Calculate the half-life for the decomposition of cyclopropane.
0.693
t1/2 = 𝑘
= 0.0458 s
5. Writing expression of rate of reaction
P dissociates to Q and R according to the reaction equation: 2P(g) → 2Q(g) + R(g)
What is the expression for the rate of disappearance of P?
−1 𝑑[𝑃]
Rate = 2 𝑑𝑡
6. From mechanism equations, deduce rate equation
Aqueous potassium iodide reacts with aqueous hydrogen peroxide in acidic solution according to the
following mechanism:

H2O2 + I- → H2O + IO- Slow

IO- + H+ → HOI Fast
HOI + H + I →I2 + H2O Fast
+ -

a. Identify rate determining step. H2O2 + I- → H2O + IO-

b. Write rate equation. Rate = k[H2O2][I-]
c. What is the unit for rate constant, k? dm3mol-1s-1 (it is second order reaction)

7. Deduce Maxwell-Bolzmann distribution curve

a. Which of the distribution curve showing

higher temperature?
Y(higher T, peak shift to right)
b. Which of the distribution curve showing
molecular speed for O2 and N2?
X: O2, Y: N2 (the lighter the particles the
faster it moves and higher kinetic
energy)
c. Mark on the curve showing reaction
with catalyst and without catalyst.
Orange line: with catalyst
Blue line: without catalyst

8. Apply Arrhenius equation

1
a. Graphical method by plotting ln k vs T to find Ea from gradient.
𝐸
ln k = − 𝑅𝑇𝑎 + ln A

Sketch graph: From the graph, an increase in absolute

temperature

will increase the rate constant,

hence the reaction rate will increase

 14

b. For two different temperatures:

A reaction happens 27 times faster at 52 oC than 22 oC. Calculate the activation energy, in kJ mol-1, for this
reaction. [Gas constant R = 8.31 J K-1 mol-1]
k E 1 1
lnk2 = Ra (T - T )
1 2 1
Ea 1 1
ln27 = ( - )
8.31 52+273 22+273
Ea = +87kJmol-1
9. Effect of catalyst, temperature and pressure to the rate of reaction and rate constant
Effect Adding catalyst Increase temperature Increase pressure
Rate of reaction Increase Increase increase
Rate constant Increase Constant constant

10. Application in industry

Process Haber Contact Ostwald Hydrogenation
Iron Vanadium oxide, Platinum and Nickel
Catalyst V2O5 rhodium

T = 400-450oC T = 450oC T = 850oC T=180oC

Condition P = 200 atm P = 1 atm P = 7 atm

Chemical equilibrium
1. Define:
a. Le Chatelier principle’s: when a change of condition is applied to a system at equilibrium, a reation
occurs, which tends to minimise the effect of the change and a new equilibrium position is attained
b. dynamic equilibrium: occurs when the rate of forward reaction is the same as the rate of backward
reaction

2. Fill in the blanks: Write expression of K, Apply Le Chatelier principle’s

Equilibrium N2(g) + 3H2(g) ⇌ 2NH3(g) 2SO2(g) + O2(g) ⇌ 2SO3(g)
∆H = - 92 kJ mol -1 ∆H = - 196 kJ mol-1
Position of Value of Kc Position of equilibrium Degree of formation of
equilibrium SO3
Increase Left decrease Left increase
temperature
Increase Right constant right increase
pressure
Increase Left constant left decrease
volume
Adding noble
gas at No change Constant No change No change
constant
volume
Adding noble
gas at Left Constant Left decrease
constant
pressure
Add catalyst No change constant No change constant

Expression of [NH3 ]2 Unit: mol-2 dm6 [SO3 ]2

Kc = [SO Unit: mol-1 dm3
Kc = [N 3 2
Kc 2 ][H2 ] 2 ] [O2 ]
 15

Expression of (PNH3 )2 Unit: Pa-2 or atm-2 (PSO3 )2 Unit: Pa-1 or atm-1

KP = P )3
KP = (P 2
Kp N2 (PH2 SO2 ) PO2

Equilibrium N2O4(g) ⇌ 2NO2(g) C(s) + H2O(g) ⇌ CO(g) + H2(g)

∆H = +58.0 kJ ∆H = +131.3 kJ.
Position of Degree of dissociation Position of equilibrium Concentration of CO(g)
equilibrium + colour
Increase Right + brown increase Right increase
temperature
Increase Left + colourless decrease Left decrease
pressure
Increase Right + brown increase Right increase
volume
Adding noble
gas at No change No change No change No change
constant
volume
Adding noble
gas at Right + brown increase Right Increase
constant
pressure
Add catalyst No change No change No change No change

Expression of [NO2 ]2 Unit: mol dm-3 [CO][H2 ] Unit: mol dm-3

Kc = [N Kc = [H2 O]
Kc 2 O4 ]

Expression of (PNO2 )2 Unit: Pa or atm PCO PH2 Unit: Pa or atm

KP = KP = PH2 O
Kp PN2O4

3. Construct ICE (initial, change, equilibrium) table for the following conditions:
Consider the equilibrium:
A(g) ⇌ B(g) + 2C(g)
Initially, a mol of A is placed in a 1.0 dm3 vessel.
a) If x mol of A decomposes to reach equilibrium with total pressure of P atm, what is the Kc and KP?
A(g) ⇌ B(g) + 2C(g)
I a 0 0
C -x +x +2x
E a-x x 2x
b) if y mol of C formed at equilibrium, what is the Kc and Kp?
A(g) ⇌ B(g) + 2C(g)
I a 0 0
y y
C - + +y
2 2
E a-
y y y
2
2
c) If 20% if A dissociated at equilibrium, what is the Kc and Kp?
A(g) ⇌ B(g) + 2C(g)
I a 0 0
C -0.2a +0.2a +2x0.2a
E 0.8a 0.2a 0.4a
 16

d) If q mol of A remains unreacted at equilibrium, what is the Kc and Kp?

A(g) ⇌ B(g) + 2C(g)
I a 0 0
C -(a-q) a-q 2(a-q)
E q a-q 2a-2q

4. Calculate/relate K for two equilibrium

The equilibrium constants, at 823 K, for two reactions are given below.
CoO(s) + H2(g) ⇌ Co(s) + H2O(g)
K1 = 67
CoO(s) + CO(g) ⇌ Co(s) + CO2(g)
K2 = 490

Calculate the equilibrium constant, at 823 K for the following reaction.

CO2(g) + H2(g) ⇌ CO(g) + H2O(g)
[H2 O] [CO2 ]
K1 = 67 = , K2 = 490 =
[H2 ] [CO]

[CO][H2 O] 1 67
K’ = [CO2 ][H2 ]
= K1 x K = 490 = 0.137
2

K ∆H 1 1
5. Apply Van Hoff equation to find K at different T: In K 2 = ( - )
R T1 T2
1
A reversible reaction involving A, B and C is shown below.
A + 2B ⇌ 2C
Given the equilibrium constant at 1000K is 2.36 mol-1dm3. If the enthalpy changes for the reaction is -20 kJ
mol-1, calculate the equilibrium constant of the reaction at 1300 K. [4m]
[The gas constant, R, is 8.31 J K-1 mol-1]
K ∆H 1 1
In K2 = ( - )
R T1 T2
1

K
2 -20x103 1 1
In 2.36 = ( -
8.31 1000 1300
)

K2 = 1.35 mol-1dm3

Ionic Equilibrium

1. Define and apply acid-base theory

Example:
Q1: Describe the properties of ethanoic acid as a Bronsted-Lowry acid.

Answer: A Bronsted-Lowry acid is a proton donor. When ethanoic acid dissolves in water, it donates a proton to the water
molecule.
Equation: CH3COOH + H2O ⇌ CH3COO- + H3O+
 17

Q2: Boric acid, B(OH)3, is an antiseptic found in some eyewash. In an aqueous solution, boric acid acts as a Lewis
acd. Explain the acidic property of aqueous boric acid.

Answer: The boron atom in boric acid has an empty 2p orbital. It can accept a lone pair of electron from the water
molecule to form a co-ordinate (dative) bond.

Polarisation of the O-H bond in the co-ordinated H2O molecule causes one of the O-H bonds to break and form

the hydroxonium ion, which makes the solution acidic:

2. Identify acid/base/conjugate acid/conjugate base

a. Identify Lewis base: BF3 + NH3 → H3N·BF3
b. Identify which reaction where OH- as conjugate acid:
O2-(aq) + H2O(l) ⇌ 2OH-(aq)
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)

3. Compare strength of acid/base or acid with conjugate base/base with conjugate acid using Ka or pKa

Example 1:
(CH3)2NH(aq) + H2O(l) ⇌ (CH3)2NH2+(aq) + OH-(aq) Kb = 5.4x10-4
NH2OH(aq) + H2O(l) ⇌ NH3OH+(aq) + OH-(aq) Kb = 9.1x10-9
a. Identify base and conjugate acid from each of the above equilibriums
b. Which of the base is stronger? (CH3)2NH(aq)
c. Which of the conjugate acid is weaker? (CH3)2NH2+(aq)

Example 2:
Acid X Y Z • Arrange the strength of acid in ascending order. Z, Y, X
pKa 3.7 4.7 7.5 • Which acid has the highest of degree of dissociation? X
• Which acid has the highest pH? Z

4. pH, pOH, Ka, Kb, Kw: calculation

a. Calculation of pH for weak acid or weak base using Ka or Kb
Example 1: Hydrazine, N2H4, is a weak base. The dissociation constant Kb of this base is 3.00x10-6 mol dm-3.
What is the pH value of a 0.100 mol dm-3 aqueous solution of hydrazine?
[OH-] = √Kb x c = √3.00x10-6x0.100 = 5.477x10-4 mol dm-3
pOH = -log 5.477x10-4 = 3.261
pH = 14-pOH = 14-3.261 = 10.7

Example 2: Carbonic acid is a weak acid with dissociation constant 4.3 x 10-7 mol dm-3. Calculate the pH of
carbonic acid with concentration 0.10 mol dm-3.
[H3O+] = c𝛼 = 0.10x4.3x10-7 = 4.3x10-8
pH = -log 4.3x10-8 = 7.4
 18

b. Calculation of pH of mixture when an acid and a base reacted

Example 1: What is the pH of the solution obtained when 300 cm3 of 0.2 mol dm-3 sulphuric acid is added to
200 cm3 of 0.4 mol dm-3 aqueous potassium hydroxide?
H2SO4 + 2KOH → 2H2O + K2SO4
MV 300x0.2
Step 1: calculate number of mole of acid = 1000 = 1000 = 0.06
Step 2: find number of mole of H+ = 0.06x2 = 0.12 mol
200x0.4
Step 3: calculate number of mole of alkali = 1000 = 0.08
Step 4: find number of mole of OH- = 0.08
Step 5: identify limited and excess reagent, since ratio of H+: OH- = 1:1, acid is excess by 0.12-0.08 =
0.04
0.04
Step 6: calculate concentration of excess H+ = 300+200 = 0.08 mol dm-3
1000
Step 7: calculate pH = log [H+] = -log 0.08 = 1.1

Example 2: A solution was prepared by mixing 100 cm3 of 0.03 mol dm-3 methanamine solution with 100 cm3
of 0.01 mol dm-3 of hydrochloric acid. Calculate the pH of the aqueous solution formed at 25oC. The base
dissociation constant, Kb for methanamine is 4.3 x 10-4 mol dm-3 at 25oC.
CH3NH2 + HCl → CH3NH3+Cl
Step 1: calculate number of mole of CH3NH2 and HCl
100x0.03 100x0.01
nb = 1000
= 3x10-3, na = 1000
= 1x10-3
Step 2: identify excess and limited reagent, since ratio of acid:base is 1:1, base is excess by 3x10-3-1x10-3 = 2x10-
3mol

2x10-3
Step 3: calculate concentration of base, c = 100+100 = 0.01 mol dm-3
1000

Step 4: calculate [OH-] = √Kbc = √4.3x10-4x0.01 = 2.07x10-3

Step 5: calculate pOH = -log 2.07x10-3 = 2.68
Step 6: calculate pH = 14-pOH = 14-2.68 = 11.3

5. Titration curve: plot graph, find buffer zone, find Ka or Kb

Example 1:
The graph below is the titration curve obtained when 50 cm3 From graph,
of 0.1 mol dm-3 ethanoic acid is titrated with a 0.1 mol dm-3
a. Find equivalence point.
sodium hydroxide solution. At V = 50 cm3
b. State indicator suitable the titration
Phenolphthalein
c. Circle buffer zone

d. Find pH when buffer capacity is maximum

*This occurs when concentration of acid
= concentration of conjugate base where
V = 25 cm3
From graph, pH = 5

e. Find Ka for ethanoic acid

[weak acid]
pH = pKa -lg[conjugate base], since [weak
acid] = [conjugate base]
5 = pKa -lg 1
pKa = 5
Ka = 1x10-5 mol dm-3
 19

Example 2:
Sketch the titration curves of pH against volume when 0.100 moldm-3 of HCl is titrated with 25.0 cm3 of
0.100 moldm-3 of the following alkaline solutions:
i. NaOH [3] ii. NH3 [3]

25

6. Buffer: buffer zone on graph, component of buffer solution, pH of buffer, effect of buffer pH when
adding acid/base, application of buffer in human blood system: phosphate buffer, carbonate buffer
and protein buffer
Example 1: An equal number of moles of two solutions are mixed together. Which pair of solutions will yield a
buffer solution?
A H2SO4(aq) and NaHSO4(aq) C NaOH(aq) and CH3COONa(aq)
B CH3COOH(aq) and NaOH(aq) D CH3COOH(aq) and CH3COONa(aq)

Example 2: Which solution forms a buffer with pH less than 7?

A Carbonic acid and sodium hydrogen carbonate C Ammonium chloride and ammonia
B Sodium hydroxide and sulphuric acid D Ammonia and ethanoic acid

Example 3: Calculate the pH of 1.0 dm3 of a buffer solution prepared by dissolving 1.0 mole of CH3COOH
and1.0 mole of CH3COONa in sufficient amount of water. [The acid dissociation constant, Ka of CH3COOH is
1.8 x 10-5 mol dm-3]
[weak acid] 1.0
pH = pKa -lg[conjugate base] = -lg1.8x10-5 -lg 1.0 = 4.7

7. Solubility product: Write expression of Ksp, find solubility product from solubility and vice versa,
predict precipitate, common ion effect

Example 1: The solubility of aluminium hydroxide, Al(OH)3, is x mol dm-3. What is the expression of the
solubility product, Ksp, of Al(OH)3?
Al(OH)3 ⇌ Al3+ + 3OH-
x x 3x
Ksp = [Al ][OH-]3 = (x)(3x)3 = 27x4
3+

Example 2: CN- ion forms an insoluble salt with Ag+ ion. The value of Ksp the salt formed is 2.3 x 10-16
mol2 dm-6 at 298 K. Calculate the solubility of the salt at 298 K.
AgCN ⇌ Ag+ + CN-
x x x
Ksp = [Ag+][CN-] = x2 = 2.3x10-16
x = √2.3x10-16 = 1.5x10-8 mol dm-3
 20

Example 3: The pH of a saturated solution of Ca(OH)2 is 12.4 at 25oC. What is the value of solubility
product, Ksp, for Ca(OH)2 at 25oC? [At 25oC, the ionic product of water is 1.00x10-14 mol2 dm-6.]

Ca(OH)2 ⇌ Ca2+ + 2OH-

x x 2x
Step 1: find pOH = 14-pH = 14-12.4 = 1.6
Step 2: find [OH-], -log [OH-] = 1.6, [OH-] = 0.025 mol dm-3
Step 3: find [Ca2+] = ½[OH-] = 0.0125 mol dm-3
Step 4: find Ksp = [Ca2+][OH-]2 = (x)(2x)2 = 0.0125x(0.025)2 = 7.81x10-6 mol3dm-9

Example 4: Will 50 cm3 of 0.1 mol dm-3 H2SO4 and 50 cm3 of 0.1 mol dm-3 Ca(NH3)2 will form a white
precipitate when mixed at room temperature? [The solubility product of CaSO4, at room temperature,
is 6x10-5 mol2 dm-6]
0.1x50 1000
Step 1: find concentration of SO42- = x
1000 50+50

Step 3: find Q = [Ca2+][SO4] = 2.5x10-3 > Ksp, therefore white precipitate will form

Example 5: Lead(II) chromate, PbCrO4, is a yellow pigment. The solubility product of PbCrO4 at 25 oC is
2.8 x 10-13 mol2 dm-6. What will happen if a few drops of an aqueous solution of lead(II) nitrate is added
to a saturated solution of PbCrO4?
PbCrO4 ⇌ Pb2+ + CrO42-
Addition of Pb(NO3)2 gives a common ion effect of Pb2+ ion which will cause the ionic product [Pb2+][CrO42-]>Ksp.
Thus, PbCrO4 will be precipitate.
[CrO42-] ions < √2.8x10-13, <5.29x10-7 mol dm-3

Phase Equilibrium
Raoult’s law: Define, Calculation
Example 1: Benzene and methylbenzene form a solution that obeys Raoult’s law. The vapour pressure of
pure benzene and pure methylbenzene are 12.7 kPa and 3.9 kPa respectively at 298 K.
Determine the vapour pressure of a solution containing 2.0 moles of benzene and 3.0 moles of
methylbenzene.
2
Step 1: find vapour pressure for benzene, Pb = XbPob = 2+3x12.7 = 5.1 kPa
3
Step 2: find vapour pressure for methylbenzene, Pm = XmPom = 2+3x3.9 = 2.3 kPa
Step 3 find vapour pressure of solution, Pt = Pb + Pm = 5.1 + 2.3 = 7.4 kPa

Example 2: Heptane and octane are mixed to form an ideal solution. At 40oC, the vapour pressure of
heptane and octane are 12.2 kPa and 4.1 kPa respectively.
Calculate the mole fraction of heptane in the vapour obtained when 0.5 mole of heptane dissolves in 1.0
mole of octane at 40oC.
0.5
Step 1: find vapour pressure for heptane, Ph = XhPoh = 0.5+1.0x12.2 = 4.07
1.0
Step 2: find vapour pressure for octane, Po = XoPoo = 0.5+1.0 x4.1 = 2.73
Ph 4.07
Step 3: find mole fraction of heptane in vapour, Xh(gas) = P = 4.07+2.73 = 0.6
h +Po
 21

Ideal solution vs non-ideal solution

1. Classify the following mixture into ideal and non-ideal solution
Mixture Intermolecular forces in pure liquid Intermolecular forces in mixture
1. Acetone + Benzene Van der Waals/Van der Waals Weaker van der Waals forces
2. Acetone + chloroform Van der Waals/Van der Waals Stronger van der Waals forces
3. Acetone + ethanol Van der Waals/hydrogen bond Stronger hydrogen bond
4. Benzene + methylbenzene Van der Waals/Van der Waals Van der Waals forces
5. Chlorobenzene + bromobenzene Van der Waals/Van der Waals Van der Waals forces
6. Chloroform + benzene Van der Waals/Van der Waals Stronger van der Waals forces
7. n-hexane + n-hexene Van der Waals/Van der Waals Van der Waals forces
8. Water + ethanol Hydrogen bond/hydrogen bond Weaker hydrogen bond
9. Water + hydrochloric acid Hydrogen bond/Van der Waals Stronger ionic interaction
10. Water + nitric acid Hydrogen bond/Van der Waals Stronger ionic interaction

Ideal solution Non-ideal solution

Positive deviation Negative deviation
4,5,7 2,3,6,9,10 1,8

2. Sketch graph of vapour pressure vs composition or temperature vs composition

Example 1: Benzene and methylbenzene form a solution that obeys Raoult’s law. The vapour
pressure of pure benzene and pure methylbenzene are 12.7 kPa and 3.9 kPa respectively at 298 K.
Draw and label, on a graph paper, the vapour pressure-composition graph for a mixture of benzene
and methylbenzene.

Example 2: Pure nitric(V) acid is a colorless liquid which forms an azeotropic mixture with water. Aqueous
nitric(V) acid shows a negative deviation from Raoult’s law.
Sketch a boiling point-composition diagram for aqueous nitric(V) acid given that nitric(V) acid boils at
78.2oC and an azeotrope mixture containing 68.2% of nitric(V) acid by mass boils at 121oC and 101kPa.
 22

3. Deduce graphs provided: type of deviation, composition in vapour/liquid phase, azeotropic (bp, composition),
product of distillation (distillate, residue)

Example 1: A solution which contains M and N is an ideal solution. The phase diagram of the mixture of M
and N at temperature T is as follows.
• Which solution M or N is more volatile?
N
• Which solution has lower boiling point?
N
• What is the physical state at the
composition of x? z?
x-gas, y-gas+liquid
• Which component will become
distillate?
N
• Sketch temperature-composition curve
from the graph

*mirror image of the vapour vs mol

fraction graph
Example 2: Water, H2O, and hydrogen fluoride, HF, form a non-ideal solution that shows deviation from
Raoult’s law. The boiling point-composition phase diagram of a mixture of H2O and HF is shown below.
a. What is the composition of vapour
when the liquid mixture containing
50% of water boils? [1m]
About 80% H2O, 20% HF

b. Determine the boiling point of

azeotropic mixture. [1m]
120oC

c. State the phase of mixture containing

20% of water at 80 oC. [1m]
Mixture of liquid and vapour
*Refer x on graph

4. Sketch graph and deduce the graph

Example: The boiling points of a mixture of liquids X and Y at different mole fractions of X are given in the table
below.
Mole fraction of X 0 0.20 0.40 0.60 0.80 1.00
Boiling point/C 97.3 90.5 88.3 87.8 88.1 100

a. State type of deviation of the solution. Positive deviation (a minimum bp)

b. Predict product when the fractional distillation of a mixture with 0.30 mole fraction of X.

*from graph, the product formed is

azeotropic mixture of 0.60 X and
0.40 Y

Y 0.30 0.60 X