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PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 1

962 /1 - CHEMISTRY SEMESTER 1 3 a) Isotopes : Atoms with the same atomic numbers (number of protons) but different mass
numbers (nucleon numbers)
CHAPTER 1 - 6 : REVISION NOTES
Element Isotopes No of proton No of neutron % of abundance
1
BY : MR CHEW CHIN KUEN CLASS : LOWER 6 TEACHERS Protium, 1H 1 0 99.0
LESSON 1 : 7 APR 2017 (FRIDAY) TIME : 6.30 - 9.30 PM
TH
Hydrogen Deuterium, D : 21H 1 1 0.99
NAME : Tritium, T : 31H 1 2 0.01
CHAPTER 1 : MATTER Oxygen-16 : 168O 8 8 98.9
17
Oxygen Oxygen-17 : 8O 8 9 1.00
1. The elementary particles (also known as sub-articles) in a carbon-12 atom Oxygen-18 : 188O 8 10 0.01

4. Mass spectrometer : instrument used to analyse components in a chemical products. It can


be used to determine
 relative isotopic mass  relative abundance of isotopes  relative atomic mass
 relative molecular / formula mass  fragments of a large molecule
a) Mass spectrum : a graph that shows the analyses of the species involved

Diagram 1.a
b) The table 1.dbelow shows the description of elementary particles and their properties.
Elementary Charge Relative
Symbol Mass (kg)
particles Coulumb unit mass
proton p +1.6022 x 10-19 +1 1.673 x10-24 1
neutron n 0 0 1.675 x 10-24 1
-19 -28
electron e- –1.6022 x 10 –1 9.11 x 10 1/1840
2. Deflection of sub-particles in electrical field and (electro)magnetic field.
Deflection in electrical field Deflection in (electro)magnetic field

i. From the graph : ratio of 35Cl+ to 37Cl+ is 100 : 33.33 or 3 : 1. From the ratio, we can
determine the relative atomic mass of chlorine :
RAM of Cl = (35 x 100) + (37+33.33) / 100 + 33.33 ; RAM of Cl = 35.5
ii. Also from the mass spectrum, we can see that there are 3 peaks at m/e 70, 72 and 74. The
abundance ratio of 3 peaks are measured at
m/e ratio Species involved Probability Percentage of abundance
a) The factors that affect the deflection of proton / electron are mass and charge  3  3  9 9
70 (35Cl – 35Cl)+ P       100%  56.25%
mass (m)  4  4  16  16 
distance of deflection  (35Cl – 37Cl)+ and   1  3  6 6
ch arg e (e ) 72  P 4  4   2  16    100%  37.5%
(37Cl – 35Cl)+      16 
Therefore, distance of deflection become further, when the mass is greater or the charge
of the species is lower.  1  1  1 1
74 (37Cl – 37Cl)+ P       100%  6.25%
 4  4  16  16 
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 2
5. Mole concept and stoichiometry CHAPTER 2 : ELECTRONIC STRUCTURE OF ATOMS

1. Important equations for calculation of hydrogen specturm.


a) Rydberg’s Equation λ = wavelength (in m)
1  1 1  n1 = ground state energy level
 RH  2  2  n2 = energy level where electron fall
 n
 1 n 2 
from compared to ground state
RH = Rydberg constant = 1.097 x 107 m-1
b) ∆E = h f ; ∆E = h c / 
h = Planck constant = 6.63 x 10-34 J s ; c = speed of light = 3.0 x 108 m s-1.
f = frequency ; f = c /  .

c) ∆H = ∆E x Na Na = Avogadro's constant = 6.02 x 1023 particles per mole

2. Emission line spectra is formed when


a) In a chemical reaction, the amount of reactants required to form certain amount of electrons falls from higher energy level to
products can be expressed by a balanced equation. For example : ground state level, where the spectrum
4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (l) formed consist of discreet lines.
Eventually, higher the energy level, the
From the equation, when 4 mol of ammonia reacted with 5 mol of oxygen, 4 mol of lines in the series converge.
nitrogen monoxide will formed, together with 6 mol of waters.
a) Different light source caused electrons
b) Using mole concepts and calculations, the moles between reactants were compared, in fall at different ground energy level.
order to determine which is the limitant or excess. For example, if 0.4 mol of NH 3 reacts Ultraviolet falls at ground level n = 1 ;
with 0.6 mol of O2, visible light falls at n = 2 ; while infrared
Reactants NH3 (g) O2 (g) falls at n = 3. Table below shows the
Stoichiometry Ratio 4 5 difference of the line spectra produced by
Reacting mole 0.4 0.6 ultraviolet and visible light.
Theory reactants 0.4 0.5
Role Limitant Excess (by 0.1)
c) Say if the reaction above were carried out in laboratory and produced 0.3 mol of NO,
therefore, 0.3 mol of NO produced is called as actual yield, the amount of product formed
in laboratory. Theoretically, the amount of NO produced is :
Reactants NH3 (g) (lim) NO (g)
Stoichiometry Ratio 4 4
Ultraviolet rays Visible rays
Reacting mole 0.4 0.3
 Produced Lyman series  Produced Balmer series
Theory reactants / products 0.4 0.4
 Can be used to determine wavelength
 Usually use to calculate ionisation
Therefore, the theoretical yield, amount of product that would result if all the limiting produced by each spectra given by
energy of hydrogen gaseous atom
reagent reacted, produced should be 0.4 mol. Therefore, there is a difference between dispersion of light
actual yield and theoretical yield. This can be then used to calculate the percentage of  In emission spectrum, electrons from  In emission spectrum, electrons from
yield higher energy level settled at n = 1 higher energy level settled at n = 2
actual yield 0.3  Series of convergence lines produced  Series of convergence lines produced
% yield   100% @ % yield   100%  75%
theoretica l yield 0.4 have higher frequency have lower frequency
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 3
3. Orbitals are spaces where there is a high probability to find an electron. CHAPTER 3 ~ CHEMICAL BONDING
Energy Number Atomic Orbital
Sublevel, l orbital, ml Interaction between elements
level, n of orbital Designation
1 0 0 1 1s
0 0 1 2s Metal-non metal Metal-metal Non-metal - non-metal
2
1 –1, 0 +1 3 2px , 2py , 2pz,
Form ionic bond Form metallic bond Form covalent bond
0 0 1 3s Electrostatic attraction Formed when metal ions Formed when electrons are
3 1 –1, 0 +1 3 3px , 3py , 3pz, forces formed between metal interact with delocalised shared when orbitals of 2
2 –2, –1, 0 , +1 , +2 5 3dxy , 3dyz , 3dxz , 3dx2-y2 , 3dz2 cation and non-metal anion. electron sea atoms are overlapped.
a) Shape of orbitals for s and p orbitals

4. Electronic configuration of an elements are written based on three rules and Principles
a) Aufbau's principle ~ electrons are filled up in orbitals from the lowest energy orbital
available ( 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < …..)
b) Pauli Exclusion's Principle ~ an atomic orbital can hold a maximum of two electrons
with opposing quantum spins
c) Hund's Rule ~ when orbitals of equal energy are available, the most stable configuration
has the maximum number of unpaired electrons with parallel spins.
Examples :
Particles Electronic configuration
Main factors affecting the intermolecular forces
7N 1s2 2s2 2p3
Lattice energy Band theory - greater the
14Si 1s2 2s2 2p6 3s2 3p2 Weak Van Der Waals' forces
Q n  Q n number of electrons
L.E.  measure the interaction
19K 1s2 2s2 2p6 3s2 3p6 4s1 delocalised , greater the
r  r conductivity. d-block
between 2 molecules.
22Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2 - LE is high when ions have Greater molecular mass,
elements will always have
high charge and small ionic greater weak VDW forces,
24Cr 1s2 2s2 2p6 3s2 3p6 3d5 4s1 higher conductivity than s-
radius. higher boiling point.
block elements.
29Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1
3-
Properties
7N 1s2 2s2 2p6
2+ - high melting points - relatively high melting - Generally have low melting
14Si 1s2 2s2 2p6 3s2
- hard yet brittle point and boiling point
3+
24Cr 1s2 2s2 2p6 3s2 3p6 3d3 - insulator at solid state, - soft, ductile and malleable. - an insulator regardless of
when molten, it can conduct - conductor in solid, or in what state of matter. (except
29Cu2O 1s2 2s2 2p6 3s2 3p6 3d10
electricity molten state for C)
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 4
1. Hybridisation in covalent molecules 2. Valence Shell Electron Pair Repulsion (VSEPR) Theories are based on 3 postulates
 sp3 hybridisation  sp2 hybridisation  sp hybridisation a) Surrounding atoms repel themselves as far as possible to occupy their own space
b) Double bond and triple bond are considered as one bond
Hybridisation sp3 sp2 sp c) bond-pair electrons - bond-pair electrons repulsion < bond-pair electrons - lone-pair
electrons repulsion < lone pair electrons - lone pair electrons repulsion
1 s and 3 p merge to 1 s and 2 p merge to 1 s and 1 p merge to
Meaning overlap with orbitals of overlap with orbitals of overlap with orbitals of Arrangement
of e- pairs
linear trigonal planar trigonal planar
4 surrounding atoms 3 surrounding atoms 2 surrounding atoms
Example CH4 BCl3 BeF2 No of lone
2 bond pair electrons 3 bond pair electrons 2 bond pair electrons
pair and bond
   0 lone pair electrons 0 lone pair electrons 1 lone pair electrons
pair electrons
Ground state
 2p  2p  2p
of element
2s 2s 2s Lewis
diagram
        
Excited state
2s 2p 2s 2p 2s 2p
Geometrical
shape
linear trigonal planar bent
Hybridised o 0
       2pz   2py 2pz Angle 180 120 < 1200
state
sp3 sp2 sp Arrangement
of e- pairs
tetrahedral tetrahedral tetrahedral
No of lone
Hybrid 4 bond pair electrons 3 bond pair electrons 2 bond pair electrons
pair and bond
diagram 0 lone pair electrons 1 lone pair electrons 2 lone pair electrons
pair electrons

Lewis
Angle 109.5 o
120 o
180 o diagram
Shape tetrahedral trigonal planar linear Geometrical
shape
tetrahedral trigonal pyramidal bent
Formation of multiple bonds in ethene ethyne
Hybridisation sp2 sp
Angle 109.5o 1070 104.50
      Arrangement
of e- pairs
trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal
Ground and 2s 2p
excited state  2p
No of lone
2s 5 bond pair electrons 4 bond pair electrons 3 bond pair electrons
pair and bond
0 lone pair electrons 1 lone pair electrons 2 lone pair electrons
pair electrons
  
Hybridised
state    2pz   2py 2pz
sp2 sp Lewis
diagram

Orbitals Geometrical
shape
trigonal bipyramidal see saw T-shape
diagram
o o 0
Angle 120 & 90 Less than 120 Less than 1200
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 5
Arrangement 4. Flow chart below shows how to determine whether a molecule is polar or non-polar
of e- pairs
trigonal bipyramidal octahedral octahedral
No of lone
2 bond pair electrons 6 bond pair electrons 5 bond pair electrons
pair and bond
3 lone pair electrons 0 lone pair electrons 1 lone pair electrons
pair electrons

Lewis
diagram

Geometrical
shape
linear octahedral Square pyramidal
o 0
Angle 180 90 < 900

Arrangement of e- pairs octahedral


No of lone pair and bond 4 bond pair electrons
pair electrons 2 lone pair electrons
5. Fajan Rule ~ ionic or covalent character can be deduced by its charge and ionic radius
Lewis diagram
Ionic compound Low positive charge Large cation Small anion
Geometrical shape square planar Covalent compound High positive charge Small cation Large anion
Angle 900 Aluminium compound - Since Al3+ has high charge and small ionic radius, therefore, it
3. There are generally 4 steps that can be used to draw a Lewis structure of a covalently has high charge density, hence high polarisation power. This will results aluminium
bonded molecules. compound to have high covalent characteristic.
Step 1 : Calculate the total number of valence electrons from all atoms in a molecule. If it is a - AlF3 is ionic compound due to the small ionic radius of F-, hence a low polarisability
molecular ion, depend on the type of ions, the number of electrons are added / subtracted. for the anion. Therefore Al3+ ion is not able to polarise the small F- hence an ionic
If the molecular ion is positively charged, the total number of electrons are subtracted, compound. AlCl3 is a covalent compound as Cl- has larger ionic radius, hence higher
however, if its negatively charged, the total number of electrons are added. polarisability. This will allow Al3+ to polarise the electron cloud of Cl- hence forming
Step 2 : Arrange all the atoms surrounding the central atom by using a pair of electron per covalent bond. This will explain why AlF3 has much higher melting point than AlCl3
bond (- 2 electrons per bond formed)
Step 3 : Assign the remaining electrons to the terminal atoms so that each terminal atom has 8
electrons [except for hydrogen] (- 6 electrons per surround atom) F- Al3+ Cl-
Step 4(a) : Place any left-over electron on the central atom. (or)
Step 4(b) : Form multiple bonds if there are not enough electrons to give the central atom - Al2O3 is an amphoteric oxide, an oxide that can act as acid as well as a base. This is
an octet of electrons due to Al2O3 is an ionic compound with high covalent characteristic, as Al3+ has high
c) iodine tetrachloride S2. Electrons bond S4a ) The 4e- remain is
charge and small ionic radius, therefore, it has high charge density, hence a high
ion, ICl4- = 4 x 2e- placed at the center atom P
Electrons left polarisation power. This will explain why Al2O3 has high melting point, yet it is
S1. Total valence = 36 - 8 = 28 e- insoluble in water.
electrons Equation of Al2O3 as base : Al2O3 + 6 HCl → 2 AlCl3 + 3 H2O
I = 7 e- ; 4 Cl = 4 x 7e- S3. e- at surroatom 4 surround atoms Equation of Al2O3 as acid : Al2O3 + 2 NaOH + 3 H2O → 2 Na[Al(OH)4]
; + 1e- accept ; = 4 x 6e- 2 lone pair electrons
Total electrons = 36 Electrons left Arrangement : octahedral
= 28 - 24 = 4 e- Shape : square planar
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 6
6. Metallic bonding ~ valence electrons of the metal atoms are delocalised to form sea of CHAPTER 4 : STATE OF MATTER
electrons and attract all the metal cations.
- Greater the valence electrons, greater the number of electrons delocalised, stronger the 1. Gas Law ~
metallic bond. Gas Law Factors Formula Graph
a) Conductivity of a substance depend on the distance between conduction band and valence
band.

Boyle's 1
P P1V1 = P2V2
Law V

b) Difference between conductor and semi conductor are compared below


Conductor Semi conductor V1 V
Charles'  2
Made of metals Made of mostly metalloid VT
Law T1 T2
Valence band and conduction band are Valence band and conduction band has a
overlapping small gaps between the band
As T increase, electrons vibrate faster, As T increased, more electrons are able to
hence impede its movement, causing the excite from valence band to conduction
conductivity activity decreased band, increasing the conductivity.
Conductivity activity can also increased Avogadro's V1 V2
by adding a dopant such as germanium or
Vn  Usually no graph is sketched
Law n1 n 2
phosphorous to semiconductor.
Based on the 3 gas laws, the relationship between P, V and T can be described as
7. Intermolecular forces between covalent molecules. P1 V1 P V
 2 2
Covalent molecules T1 T2

Avogadro's Law Boyle's Law Charles' Law


Hydrogen bond Weak Van Der Waals' forces 1
Vn V VT
P
As conclusion : nT ; nT ; where R is gas constant, 8.31 J mol-1 K-1
Molecular mass (or size) V VR
P P
Polar molecule Non-polar molecule Ideal Gas Equation : PV = nRT
(higher dipole moment) (lower dipole moment)
Given density, d = m/ V ; therefore dRT
MR 
Straight chain (higher P
total surface area)
Branched chain (lower
total surface area)
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 7
2. Partial pressure : pressure exerted by each individual gas
a) When a liquid has high vapour pressure, it is
a) Dalton's Law partial pressure : In a gaseous mixture that is at equilibrium, total pressure is
easier to vapourise. For such liquid, it is
the summation of the partial pressure exerted by each individual gas
called as a volatile liquid, a liquid which
Ptot = PA + PB + ….
vaporised easily at room temperature. In
b) For the partial pressure of each gases, it can be calculated from the formula
another words, for a liquid with high vapour
nA
nA  nB
 xA PA = xA . Ptot pressure, it will have a low boiling point.
b) Boiling is achieved when the pressure of the
3. In the Maxwell distribution of speed (or energy), two factors are used to explain. system is the same with external pressure.
- temperature - molecular mass Therefore, if the external pressure is
 Area at 3 temperature are the same, indicating number lowered, the pressure of system will also be
of particles are the same at 3 diff temp, where each lowered, hence a lower boiling point.
distribution graph shows its peak at middle, indicate - 6. Primitive unit cell
most molecules travel at average speed (energy) but Rhombohedral Tetragonal Triclinic
little molecule travel at high speed (energy)
 As T increased, peak become lowered while base
become broader, indicate lesser particles travel at
average peak, but more molecule travel at higher speed.
 Peak shift to the right meaning at higher T, molecules
has higher average speed, and molecules with higher
speed also increased gradually.
4. Deviation of gases from ideal behaviour
a) All gases obey ideal gas law at high temperature and low pressure
Monoclinic Orthorhombic Hexagonal
b) Gases are ideal due to these characteristic
- no intermolecular forces (attraction or repulsion) between particles
- gases has negligible volumes
c) Graph below shows the relationship between the factors of PV/RT against P for ideal
gases and all other gases.
- When P initially increased,
attraction forces take place between
particles. As a result, attracted
particles collide less frequently
with wall of container and caused
the pressure to be lesser than
expected. Therefore, PV/RT < 1,
hence a negative deviation.
- Greater the molecular mass,
greater the weak Van Der Waals
forces, stronger the attraction force
No of particles / unit cell No of particles / unit cell
No of particles / unit cell
- As pressure gradually increased, repulsion forces started to take place between particles. = (8 x corner) + 1 body = (8 x corner) + 6 face
= 8 x corner
As a result, particles will repulse each other greatly, and caused the collision of particles to center center
1 1 1 1
collide more rapidly, causing PV / RT > 1, hence a positive deviation.  8  8  1 (1)  8  6
5. Vapour Pressure ~ pressure exerted when vapour particles collide with the wall of a 8 8 8 2
closed container. Saturated vapour pressure is achieved when the rate of vaporation is the = 1 particle / unit cell
= 2 particles / unit cell = 4 particles / unit cell
same with the rate of condensation.
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 8
7. Allotropy is elements that can exist in more than one structure under the same state of CHAPTER 5 : KINETIC CHEMISTRY
matter. For examples :
a) oxygen can exist as oxygen gas (O2) gas and ozone (O3) gas 1. Kinetic chemistry ~ study of changes of concentration in a chemical reaction at a given
b) carbon (C) can exist as three allotropes : diamond, graphite and fullerene time. Says a chemical reaction take place below x A (aq) → y B (aq)
Diamond (sp3 hybridised) Graphite (sp3 hybridised) a) rate of reaction of A and B can be expressed below
d[A] d[B]
rate   rate 
dt dt
2. 3 postulates for particles to react from the angle of kinetic theory :
a) Particles must collide in order to react
- This is generally influenced by 2 factors, concentration and temperature. Higher the
concentration, greater the number of particles collide, higher the rate of reaction.
- Higher the temperature, greater the kinetic energy of particles, faster the particles move
- contain one unhybridised orbital with an and collide with greater energy, hence higher the rate of reaction.
- no delocalised electron (insulator)
electron delocalised (conductor) b) Particles collide at the right orientation :- when 2 particles of reactant collide, it must be
- use as diamond cutter, jewelery - use as electrode, lubricant collide at the right position, in so that the reaction can take place. Example :

8. Phase diagram - a graph of pressure against temperature which explain how solid, liquid
and gas are formed between each other.
a) Phase diagram of water, H2O b) phase diagram of carbon dioxide, CO2

c) Particles collides with minimum amount of energy called as activation energy. Activation
energy is the minimum amount of energy required to initiate a chemical reaction.
3. During a chemical reaction take place, a substance will be formed during chemical
reaction. For example, in the hydrolysis of haloalkane :

b) Note in the phase diagram of water, the melting curve slopes to the left with increasing
pressure showing that as the pressure is increased, the melting point of ice decreases
slightly. This is unusual because an increase in pressure usually favours the formation of
solid. However, this behaviour is due to ice having an open structure. As the pressure
exerted is increased, the hydrogen bonds between the H 2O molecules in ice are broken
down, changing the ice into a denser liquid phase which occupies a smaller volume. Same a) From the reaction, is called as intermediate, a substance formed during
things applied when temperature increased. Hydrogen bond between ice broken, and the chemical reaction, but will not formed as a product
open structure of ice broken. As a result, distance between water molecules become 4. - Rate law is a way to expresses the relationship of the rate of a reaction to the rate constant
closer, hence volume decreased, which increase the density of water. and the concentrations of the reactants raised to some powers
c) For carbon dioxide, its solid is called as dry ice, which is used as refrigerant. Fumy effect - Rate constant, k, is the proportionality constant of the reaction, in which the value remain
is due to as dry ice sublimed when surrounding heat is absorbed, surrounding temperature constant under constant temperature
decreased. As a result, water vapour from the surrounding condensed hence form the - order of reaction, x and y, is the power to which the concentration of the reactants (in this
fume. case, [A] and [B] respectively) is raised to in the rate equation
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 9
Example of calculation to determine order of reaction
Zero order First order Second order O2 (g) + 2 NO (g) → 2 NO2 (g)
Rate rate = k [A]0 1 rate = k [A]2 or The rate equation, expressed in general form, is
rate = k [A]
equation = k rate = k [A] [B] rate = k [O2]x [NO]y
Unit of k -3 -1
mol dm s s-1 mol-1 dm3 s-1 Note that the order of reaction cannot be determined directly from the
[reactant] [reactant] [reactant] stoichiometry of the reaction. To find out the orders of reactant with respect to each O 2 and
NO, we run series of experiments, starting each one with a different set of reactant
[A]0 [A]0 concentrations and obtaining an initial rate in each case.

Graph of
Initial concentration of reactant Initial rate
Exp
[reactant]
k = - gradient O2 / mol dm-3 NO / mol dm-3 (mol dm-3 s-1)
[A]0/2 [A]0/2 1 1.10 x 10 -2
2.50 x 10-2 2.40 x 10-3
vs time
-2
2 2.20 x 10 2.50 x 10-2 4.80 x 10-3
[A]0/4 [A]0/4 -2
3 1.10 x 10 5.00 x 10-2 9.60 x 10-3
time From each experiment, the rate equations are expressed individually, where
t½ t½ time t½ 2t½ time
rate rate rate Experiment 1 : 2.40 x 10-3 = k (1.10 x 10-2)x (2.50 x 10-2)y
Experiment 2 : 4.80 x 10-3 = k (2.20 x 10-2)x (2.50 x 10-2)y
Experiment 3 : 9.60 x 10-3 = k (1.10 x 10-2)x (5.00 x 10-2)y
Graph of Comparing Exp 2 to Exp 1 : 4.80 x 10-3 = k (2.20 x 10-2)x (2.50 x 10-2)y
rate gradient = k 2.40 x 10-3 = k (1.10 x 10-2)x (2.50 x 10-2)y
against 2 = (2)x
[reactant] Order of reaction with respect to O2 ; x = 1
Comparing Expe 3 to Exp 1 : 9.60 x 10-3 = k (1.10 x 10-2)x (5.00 x 10-2)y
2.40 x 10-3 = k (1.10 x 10-2)x (2.50 x 10-2)y
[reactant] [reactant] [reactant]
4 = (2)x
1 1 Order of reaction with respect to NO ; x = 2
Equation [A]0 – [A]t = k t ln [A]0 – ln [A]t = kt   kt From the order of reaction deduced, the rate equation is rate = k [O2][NO]2.
[A] t [A]0 The overall order of reaction = 1 + 2 = 3
Half-life Using any experiment, rate constant can be calculated. For example, in experiment 1
t½ = [A]0 / 2k t½ = 0.693 / k t½ = 1 / k [A]0
equation 2.40 x 10-3 = k (1.10 x 10-2) (2.50 x 10-2)2
[A]t against time ln [A]t against time 1 / [A]t against time k = 349 mol-2 dm6 s-1.
[A]t ln [A]t 1 / [A]t
5 Chemical reactions may occur in one way reaction or a reversible reaction. In a one way
reaction, process may be taken in multiple steps, and therefore irreversible back to the
reactants, as they might involve in steps that required higher activation energies. Example
2 NO (g) + O2 (g) 2 NO2 (g)
k = gradient k = gradient k = gradient Mech-
Linear Reaction Equation Rate equation
plot anism
Step 1 2 NO slow
  N 2 O 2 rate = k [NO]2
N 2O2  O2
Step 2 rate = k [N2O2] [O2]
fast
 2 NO 2
time time time
In a mechanism, slow step is rate determining step. Therefore, the rate equation for the
overall reaction can be written as rate = k [NO]2.
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6. Generally, the rate of reaction increased with temperature as it affect the rate by increased CHAPTER 6A : CHEMICAL EQUILIBRIUM
the rate constant of the reaction. The dependence of the rate constant of a reaction on
temperature can be expressed by using Arrhenius equation 1. Dynamic equilibrium ~ In a reversible reaction, a system is to say reaches dynamic
E k = rate constant A = Arrhenius constant equilibrium when the concentration of reactants and products remain constant, while the
 A T = temperature EA = activation energy reaction is ongoing at the rate of forward reaction is the same as the rate of backward
k  Ae RT
R = gas constant (8.31 J mol-1 K-1) reaction.
a) For example : w A (aq) + x B (aq) ↔ y C (aq) + z D (aq)
a) When Arrhenius equation is derived, the equation can be re-expressed as :
E E 1 equilibrium constant of concentration, [C]y [D]z
ln k  ln A  A ; rearrange the equation ln k   A  ln A KC 
RT R T [A]w [B]x
b) When a graph of ln k against 1/T (in Kelvin) is plotted, the gradient of the graph can be b) If a gaseous system is involved, not only it can be expressed as Kc, but it can also be
used to calculate the activation energy of the reaction. expressed as equilibrium constant of partial pressure, Kp
c) Activation energy can also be calculated when the rate constant at two different N2 (g) + 3 H2 (g) 2 NH3 (g)
temperature.
Equilibrium constant of concentration, KC Equilibrium constant of partial pressure, KP
 E   E  k E 1 1
ln k1  ln k 2    A  ln A     A  ln A   ln 1  A    [ NH3 ] 2 (PNH 3 ) 2
 RT 1   RT 2  k 2 R T
 2 T1 KC  KP 
[ N 2 ][ H 2 ]3 (PN 2 ) (PH 2 ) 3
7. Catalyst is a substance added to a chemical reaction to alter the rate of reaction.
- catalyst is added to lower the activation energy by providing an alternative route for the 2. Method of calculating Kc and Kp for examples of reaction are stated below
reaction to take place. However, amount of product will remain the same. a) Dissociation of phosphorous (V) pentachloride
- the route provided by catalyst is specific. However, even without the addition of catalyst, PCl5 (g) ↔ PCl3 (g) + Cl2 (g)
the reaction will still take place, its just that catalyst will make reaction occur faster. Initial mol 1 mol 0 0
degree of dissociation,  -  +  +
a) Energy profile of endothermic and exothermic reaction with and without the addition of
catalyst is described in the diagram below At equilibrium 1-  

If calculating KP of reaction
If calculating Kc of 1. First calculate their mol fraction
total mol = 1 -  +  +  =1+
reaction
XPCl5 = ( ) XPCl3 = ( ) XCl2 = ( )

2. The find its partial pressure (total pressure = P tot)

( )( ) PPCl5 = ( )Ptot PPCl3 = ( ) Ptot PCl2 = ( ) Ptot

( ) 3. The substitute all partial pressure into Kp

KP =
b) Autocatalyst is formed when product itself act as catalyst. An example of reaction for
autocatalyst is the reaction between sodium ethanedioate and potassium manganate (VII) b) Another example is the dissociation of dinitrogen tetraoxide, N 2O4 (g) to form nitrogen
2 MnO4- (aq) + 5 C2O42- (aq) + 16 H+ (aq) → 2 Mn2+ (aq) + 10 CO2 (g) + 8 H2O (l) dioxide gas, NO2 (g)
N2O4 (g) ↔ 2 NO2 (g)
Initial mol 1 mol 0
degree of dissociation,  -  +2
At equilibrium 1- 2
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If calculating KP of reaction 4. Temperature is the only factor that can change the equilibrium constant of a chemical
If calculating Kc of 1. First calculate their mol fraction equilibrium. This can be deduced using Van't Hoff equation, which is expressed below
reaction total mol = 1 -  + 2 =1+ H ∆H = enthalpy change of reaction
ln K   C R = gas constant (8.31 J mol-1 K-1)
XN2O4 = ( ) XNO2 = ( ) RT T = temperature in Kelvin (x 0C + 273)
2. The find its partial pressure (total pressure = P tot) a) Based on the expression above, if a graph of ln K against 1/T is plotted, a liner graph will
be obtained. Using this graph, the enthalpy change of a chemical reaction can be
( ) PN2O4 = ( )Ptot PNO2 = ( ) Ptot
determined. Table below summarised the graph of endothermic and exothermic process
( ) 3. The substitute all partial pressure into Kp
Exothermic process Endothermic process
KP =
K K
3. Le Châtelier’s principle states that if an external stress is applied to a system at
equilibrium, the system adjusts in such a way that the stress is partially offset as the
system reaches a new equilibrium position.
a) Concentration :- changes of concentration will shift position to counter the changes
toward the concentration of the substance involved. However, Kc and Kp will remain
unchanged.

System is Temperature / K Temperature / K


disturbed -
Given A + B ↔ C + D ∆H = - ve Given A + B ↔ C + D ∆H = + ve
added  at
right side. Increasing temperature decreased K Increasing temperature increased K
ln K ln K
Equilibrium will shift to the left to balance back the equilibrium. + gradient = - ∆H / R - gradient = - ∆H / R
∆H = negative ∆H = positive

b) Pressure : If the pressure of the system is increased, equilibrium will adjust to decrease
the pressure by shifting to the position with less total mol of gas. 1/T / K-1 1/T / K-1
- If the pressure of the system is decreased, equilibrium will adjust to increase the
pressure by shifting to the position with more total mol of gas. b) At two different temperature, ∆H of the reaction can also be calculated using the formula
i. When an inert gas is added to an equilibrium system under constant volume,
equilibrium will not be disturbed, hence position of equilibrium will not shift. K 2 H  1 1 
ln    
ii. When an inert gas is added to an equilibrium system under constant pressure,
the total pressure will not change , and adding inert gas will decrease the partial
K1 R  T1 T2 
pressure of the gaseous mixture, hence position of equilibrium will shift its position
to increase the pressure, therefore position with more total mol of gas.
However, regardless how the pressure changes, KC and KP will remain constant.
c) Temperature :- when temperature increased, system will respond to decrease the
temperature - by shifting to the direction of decreasing temperature, hence an
endothermic path. Conversely, when temperature decreased, system will respond to
increase the temperature - by shifting to the direction of increasing temperature, hence
an exothermic reaction
PRE–U STPM CHEMISTRY I SEMESTER 1 I Chapter 1 - 6 - Short Note Revision Kursus Kecemerlangan STPM Chemistry I  Chew Chin Kuen | 12
+ -
CHAPTER 6B : ACID-BASE AND SOLUBILITY EQUILIBRIA 3. Ionic product of water is derived from the equation H 2O (l) ↔ H (aq) + OH (aq). From
+ -
the reaction, ionic product of water, Kw = [H ] [OH ]
1. Bronsted-Lowry acid : substance which donate proton to base a) o -14 2 -6
At 25 C, Kw = 1.0 x 10 mol dm . Using this figure, Kw is expressed as pKw.
Bronsted-Lowry base : substance which accept proton from acid. Therefore, the equation Kw = [H+] [OH-] is applied with negative logarithm.
Lewis acid : substance which accept lone pair electron from a base -lg 1.0 x 10-14 mol2 dm-6 = -lg [H+] + (-lg [OH-] ) @ 14 = pH + pOH
Lewis base : substance which donate lone pair electron to an acid.
b) Under certain derivation, Kw = Ka x Kb
From the angle of Bronsted-Lowry acid-base theory :
CH3COOH (aq) + H2O (l) ↔ CH3COO- (aq) + H3O+ (aq) 4. Indicator is a weak organic acid added to a solution to show acidity of a solution. A few
B.L acid B.L base conjugate base conjugate acid example of indicator are shown below
Indicator Acid Basic End point colour
From the angle of Lewis acid-base theory : Methyl orange Reddish orange Yellow Orange
Bromothymol blue Yellow Blue Green
Phenolphthalein Colourless Pink purplish Light pink
In the titration curve section shall discuss further of how its applied
2. For a dissociation of a weak acid/base, the strength of an acid /base can be measured 5. Buffer solution ~ solution where pH does not change much when a little acid or base is
using dissociation constant of acid, Ka or base, Kb. added to the solution
Equation HA (aq) + H2O (l) H3O+ (aq) + A- (aq) a) Acidic buffer [Eg : CH3COOH (weak acid) and CH3COONa (salt of conjugate base) ]
Initially concentration c (unknown) 1 (constant) 0 0 Basic buffer [Eg : CH3NH2 (weak base) and CH3NH3Cl (salt of conjugate acid) ]
Degree =  -c +c +c b) Role of buffer solution :- In aqueous solution, both ethanoic acid and sodium ethanoate
dissociate accordingly to the following equations :
At equilibrium c(1-) c c
CH3COOH (aq) + H2O (l) ↔ CH3COO- (aq) + H3O+ (aq)
[H 3O +] [A ] Substitute the concentration of [H3O+], [A-] and [HA] into the CH3COONa (aq) → CH 3COO- (aq) + Na+ (aq)
Ka  When a little acid is added to the solution, H+ added will react with CH3COO- to form
[HA ] equation
CH3COOH, therefore does not affect the concentrated of H+ in the buffer system. When
(c)(c) Since  is very small (less than 0.05 is consider small), a little base is added to the buffer solution, OH- will react with H+ in system, where
Ka 
c(1  ) therefore we assume that 1   ≈ 1. H+ + OH-  H2O. Therefore decreased the concentration of H+. Based on Le Chatelier
Principle, equilibrium in (1) will shift to the right, and form H+ to compensate the H+
(c)(c) Therefore, [H3O+] = K a  c
Ka  Since [H3O+] = c  lost in the system.
c c) The equation used for determining pH of buffer solution with the appropriate ratio of
2 + weak acid and its conjugate base salt used is :
Ka = c  pKa = lg Ka and pH =  lg [H3O ] [ weak acid ] [ weak base]
pH  pK a  lg pOH  pK b  lg
Equation M (aq) + H2O (l) +
MH (aq) + OH (aq) - [conjugate base] (salt ) [conjugate acid ] (salt )
At equilibrium c(1-) c c
5. Dissociation of polyprotic acid take place in stages of neutralisation. For example in the
+
[MH 2 ] [OH ] 
Substitute the concentration of [MH2+], [OH-] and neutralisation of sulphite acid, H2SO3, with NaOH, it undergoes 2 stages of reaction
Kb  Stage 1 : NaOH (aq) + H2SO3 (aq) → NaHSO3 (aq) + H2O (l)
[MH ] [MH] into the equation
Stage 2 : NaOH (aq) + NaHSO3 (aq) → Na2SO3 (aq) + H2O (l)
(c)(c) Since  is very small (less than 0.05 is consider small), Each stage of neutralisation at equal volume. Another example is the reaction of HCl with
Kb 
c(1  ) therefore we assume that 1   ≈ 1. sodium carbonate, Na2CO3.
Stage 1 : HCl (aq) + Na2CO3 (aq) → NaHCO3 (aq) + NaCl (aq)
(c)(c) (c)(c)
Kb  Since [OH] = c  Kb  Stage 2 : HCl (aq) + NaHCO3 (aq) → NaCl (aq) + H2O (l) + CO2 (g)
c c
Kb = c 2 pKb = lg Kb Kb = c 2
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6. - Solubility is the quantity of solute that dissolved in unit volume of saturated solution at CHAPTER 6C : PHASE EQUILIBRIA
a given temperature
- Solubility product, Ksp, of a sparingly soluble electrolyte is the product of the 1. Ideal solution ~ mixture of two solutions that obey Raoult's Law. Two characteristics of
concentrations of the ions in a saturated solution at a given temperature ideal solutions are :
a) Intermolecular forces between two solutions and mixing solutions are the same
b) No heat absorb or liberated when mixed. Therefore, total volume = summation of volume
of two solution mixture.

In vapour (Dalton's Law)


P A = xA  P T
PT = PA + PB.

In liquid (Raoult's Law)


PA = xA  PA0

2. Diagram of vapour pressure composition graph and boiling point composition graph.
Vapour Pressure / kPa Boiling point / oC
a) The common ion effect is the suppression of the ionization of a weak acid or weak base
by the presence of a common ion from a strong electrolyte. For example : gas
Mg(OH)2 (aq) ↔ Mg2+ (aq) + 2 OH- (aq) liquid

When strong base, NaOH, is added to Mg(OH)2 aqueous solution, concentration of OH- is
high, therefore equilibrium shift to left, therefore decrease solubility.
b) At a particular temperature, Ksp value indicates the maximum product of ion
concentrations in solution at equilibrium. MX (s) M+ (aq) + X- (aq) liquid
+
Ionic product, Q = [M ] [X ] - gas
a) If ionic product, Q = Ksp → The system is at equilibrium and the solution is saturated,
formation of precipitate is observed. 0 mol fraction composition 1 0 mol fraction composition 1
b) If ionic product, Q > Ksp → The system is not at equilibrium and the solution is
supersaturated. The concentrations of the ions in solution are too high and thus the salt 3. Fractional distillation ~ technique use to separate 2 miscible liquids.
will precipitate. Boiling point / oC When a mixture at composition a is brought
c) If ionic product [M+] [X-] < Ksp → The system is not at equilibrium and the solution to fractional distillation, it will first boil at
is not saturated (ie. more solid can dissolve until equilibrium is achieved), so no gas temperature T1, and vapour mixture is at
precipitate formed T1 composition b, which then condensed at
Example 1: Will a precipitate form when 50 cm3 of 0.050 mol dm-3 AgNO3 is added to 50 temperature T2. Fractional distillation
cm3 of 0.10 mol dm-3 KBrO3? [Ksp AgBrO3 = 6.0 x 10-5 mol2 dm-6] T2 continue at the second plate, where liquid
For [Ag+] in mixture, For [BrO3-] in mixture, mixture boiled at T2 and gives vapour
M1V1 = M2V2 (total) (0.050)(50) M1V1 = M2V2 (total) (0.10)(50) T3 composition at c, then condensed at
M2  M2  liquid temperature T3. Note that concentration of A
(50  50) (50  50) keep increasing as mixture distillate where
M2 = 0.025 mol dm-3 M2 = 0.050 mol dm-3 vaporation - condensation keep on occurring
' a b c
Since AgBrO3 (s) ↔ Ag+ (aq) + BrO3- (aq) ; Therefore, Q = [Ag+][BrO3-] 0 mol fraction composition A 1
until pure A is distillate, leaving pure B as
Q = (0.025)(0.050) = 1.25 x 10-3 mol2 dm-6 residue.
Since Q > Ksp ; therefore mixing both solution will form precipitate of AgBrO 3.
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o o
Deviation from Ideal solution behaviour. boiling point / C boiling point / C
Negative deviation Positive deviation
HCl – H2O ; HNO3 – H2O ; H2SO4 – Propanol – H2O ; ethanol – H2O ;
Example HCOOH ; phenol – aniline ; acetone ethanol – toluene ; ethanol and Boiling
(CH3COCH3) – CHCl3 benzene point-
Intermolecular forces between A---B Intermolecular forces between A---B compo-
Happen sition
molecules are stronger than in molecules are weaker than in between
when curve
between pure A---A and pure B---B pure A---A and pure B---B
Partial Since the intermolecular forces are Since the intermolecular forces are 0 1 0 1
pressure stronger in A---B ; the partial vapour weaker in A---B ; the partial vapour Composition by % mass A Composition by % mass A
of pressure are lower than expected in pressure are higher than expected in
mixture Raoult’s Law Raoult’s Law
Fractional distillation of negative deviation
Since the intermolecular forces are Since the intermolecular forces are
boiling point / oC
Heat stronger, A --- B are more stable than weaker, A --- B are less stable than st
1 Distillate : 1st Distillate :
changes their individual forces, thus the their individual force thus the process
Pure B Pure A
process is exothermic is endothermic
2nd distillate : 2nd distillate :
HCl and H2O Azeotropic mixture Azeotropic mixture
The forces hold between HCl – HCl Ethanol, C2H5OH and H2O
are pure Van Der Waals forces The intermolecular forces between Residue : Residue :
whereas the forces between H2O – ethanol – ethanol are hydrogen Pure A + impurities Pure B + impurities
H2O are pure hydrogen bonding bonding and same goes to between
When HCl and H2O are mixed water – water. 0 1
Reasons
together, it will ionised to form However, when this 2 solutions are Composition by % mass A
HCl + H2O  H3O+ + Cl- mixed, the hydrogen between water
The ionic interactions between are broken by ethanol and reduce the Fractional distillation of positive deviation
hydrated ions are stronger than both intermolecular forces formed between boiling point / oC
Van Der Waals forces and hydrogen ethanol – water. st
1 Distillate : 1st Distillate :
bond. Azeotropic mixture Azeotropic mixture
Since mixing the solution causes a Since mixing the solution causes a 2nd distillate : 2nd distillate :
Volume
stronger attraction forces formed weaker attraction forces formed Pure B Pure A
of
between A---B ; so when 50 cm3 A + between A---B ; so when 50 cm3 A +
mixture
50 cm3 B < 100 cm3. 50 cm3 B > 100 cm3. Residue : Residue :
kPa kPa Pure A + impurities Pure B + impurities

0 1
Vapour Composition by % mass A
pressure
compo- Azeotropic mixture is a mixture of two solution that has a constant boiling point, which
sition the liquid state is at equilibrium with gaseous state
curves

0 1 0 1
mol fraction of A mol fraction of A

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