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CM1401 Notes

Thanks to Dr Linda Sellou, NUS Department of Chemistry. For her physical


chemistry lectures, slides and tutorials from which this note is based on.
Also thanks to lecturer Fun Man for this videos and slides on organic chemistry
Accuracy of notes not guaranteed, so refer to textbook to be sure of concepts.

Miscellaneous
1. Always change eV to J before calculations
2. Accuracy of answer depends on the decimal place of the data.
a. Do not give more accurate answers, unless it is unreasonable to do
so.

Equations
E=hv=

1. Energy of photon:

hc

a. Used to find wavelength of light absorbed or emitted

eV =

2. Electron volt:

Joules of object
Charge of an electron

n=13.6

3. Bhors equation:

2
Z2
18 Z
eV
=2.18
10
J
n2
n2

( )

( )

a. Used to find energy level of a shell


b. Only applicable when only 1 electron is present
4. Bond order =

Number of electronsbonding orbitalsnumber of electronsantibonding orbitals


2
a. Used to determine stability of molecule formed and bond strength
5. Equilibrium constant and reaction quotient =
Stoichiometry of product 1

Stoichiometryof product 2

a Product 1
a Product 2
Stoichiometry of reactant 1
Stoichiometryof reactant 2
aReactant 1
a Reactant 2
a. a is the activity of the compound. How much it contributes to the
reaction.
b. K and Q shows the ratio of products and reactants at specific times
of a reaction
c. Equilibrium is when time = infinity
6. Ideal Gas Law:

pV =nRT

a. Where R = 8.314 J/K.mol


7. Equations to find pH
a. pH =

+
H

lg

conjugate base
acid

b. pH =

p K a+ lg

c. pH =

p K w pOH
U =w+ q

8. Change in internal energy:


a. w is work, q is heat
9. Energy flow due to work:

w=p ext V

H=U + pV =q+V p

10.Enthalpy:

H =q p =C p T =m c p T =n c p ,m T

a. At constant pressure:

b. The subscript p indicates constant pressure


c. The subscript m stands for molar, to show that the c is used for
molar heat capacity

Cp=

11.Heat capacity of an object:

q
T

a. Used to find energy needed to cause a certain change in


temperature
12.Enthalpy change of a reaction:

H r = vi H f ,i ( products) v i H f ,i (reactants)
i

a.

vi

is the stoichiometric coefficient

13.Kirchhoffs Law:

H or ( T ' ) = H or ( T )+ C op ,r (T ' T )

a. Used to find enthalpy change of reaction at a temperature different


from given data
i. New temperature T from given data at T
ii.

C op ,r = vi C op ,i ( products) v i C op ,i (reactants)
i

b. Only possible when heat capacity is given, else use assumption that
enthalpy is constant over a range of temperatures
O

Strans =

14.Entropy change of phase transition:

H Otrans
T trans

a. Usable only for phase transition at constant pressure at transition


temperature
b.

Strans =S surrounding

only at phase transition

15.Entropy change of surroundings:

S surr=

H Or
T surr

16.Entropy change of a reaction:

SOr = vi SOi ( products ) v i SOi (reactants)


i

17.Change in Gibbs Free energy ( G r )


a. From enthalpy and entropy:

Gr = H r T S r

Gr = vi G f ,i ( products) v i Gf ,i (reactants)

b. From formation:

c. From standard conditions and Q:

Gr =Gr + RT lnQ

i. R = 8.315 J/K.mol

Gr =0 :

d. At equilibrium, Q = K,

e. From cell potential difference:


f.

GOr =RT ln K

Gr =nF Ecell

Gforward = Gbackward

From reverse reaction:

18.Transition temperature for Gibbs free energy:


a. The temperature where

G Or

19.Standard potential for voltaic cell:

Hr
T transition =
O
Sr

changes sign
O
cell

E =Ecathode E anode

a. Data depends on temperature


b. Data given is always from reduction perspective, so need change
sign
20.Nernst equation:

Ecell =Ecell

RT
ln Q
nF

a. F = 9.6485 x 104 C/mol


21.Integrated rate law
a. Zero order:

[ A ] t=kt + [ A ] 0

a. First order:

ln [ A ] t=kt + ln [ A ]0
1
1
=kt+
[ A ]t
[ A ]0

b. Second order:

22.Arrhenius equation:
a. Where

Ea
1
R
ln k =
+ ln A
T

is the collision frequency factor that is affected by

Ea

temperature, and

is the activation energy

23.To substitute intermediate with original reactant in the rate law:

rate=

k intemediatek reactant fwd n


[ B]
k reactant bwd

a. Where B is the original reactant, and n is its order of reaction


b. Basically sub in
i. Where

[A] =
k reactant fwd
k reactant bwd

formation of

k reactant fwd n
[ B]
k reactant bwd

is the net formation of


is reversible

if the

ii. Else just

[ A ] =k reactant [ B ]

Physical Chemistry
Electrons in an Atom
1. A diffraction pattern is formed when a wave splits up after passing through
a crystal
2. Electron are shown to behave like waves when passed through an
Aluminium atom, as there is the formation of a diffraction pattern, much
like one produced by X-rays
a. As in there is clearly wave interference, proving the wave-particle
duality
3. The Bhors model of electron shells is useful in explaining why the light
emitted by Hydrogen is different from the light emitted by Helium
a. Electrons absorb different wavelength of light when excited and
produce a different colour upon release
b. Electrons can only be excited and change shells by absorbing or
emitting a specific quanta of energy (photon)
i. Quantum is the minimum amount of any physical entity
involved in an interaction
ii. Photon can refer to light and any other electromagnetic
radiation
4. Bhors model is limited as it cannot predict the light spectrum of other
atoms, working for only 1 electron atoms or ions.
a. Bhors assumes all the sublevels in a shell have the same energy
b. There are additional electron forces that complicate the prediction
i. Electron-electron repulsion
ii. Effective nuclear charge
5. Energy of a particle can be written in Joules or electronvolts
a. eV is the amount of energy gained by the charge of a single
electron moved across an electric potential difference of one volt
b. Remember to write the correct units!
6. Schordinger says that we do not need to know the exact position of the
electron, just use the wave properties of the electron to find the atomic
orbital (psi), and this the probability of finding the electron (psi squared)
7. An electron has 4 numbers
a. Principle is the shell it belongs in
b. Angular is the shape of its orbital
c. Magnetic is the orientation of the shape
d. Spin is the direction of electron spin
8. Pauli exclusion principle
a. No two electrons can have the same set of quantum numbers
i. Electrons in the same orbital have the same energy but
opposite spins
9. Probability density (psi squared) does not equal the probability of electron
position.
a. Psi squared is: Probability / Volume
10.R2(r) = Psi squared
11.Radial distribution function P(r) is the probability of finding the electron on
the surface of circle with radius r.
a. P(r) is the sum of all the Psi squared at all points on the circle
12.The boundary of space of an electron is where it spends 90% of its time
13.The graph of P(r) shows that they highest probability of finding the
electron is not at or very near the nucleus

14.With the 2s and 3s orbitals, there are nodes where there is a 0 probability
of finding an electron
15.The bigger an orbital, the further away the electron spends most of its
time.
16.The energy is negative in an energy level diagram, as it is convention
a. 0 is taken as a point infinitely away from the atom
17.When an electron drops down from the excited state, to a lower shell it
can drop in two ways
a. It can drop directly back to ground state, release the same
wavelength it absorbed
b. It can drop by steps, to an intermediate electron shell, releasing the
corresponding wavelength for the energy gap. Thus this produces
visible light (or not).
18.There is a splitting of energy level within the shell, which gives rise to the
p orbital having more energy than the s orbital.
a. Energy level can differ between different elements, due to nuclear
charge
b. Or within the shell, due to shielding effect (repulsion) and
penetration effect (orbital shape)
i. Penetration effect is where the electrons in the s orbital have
a probability of being close to the nucleus, closer than the s
orbital below it, effectively penetrating the shielding effect.

Properties of atoms
1. Atomic radius
a. Decreases along the period
i. Additional proton increases nuclear charge
ii. Increase is greater than loss from electron-electron repulsion
Even when electron is added to another subshell
iii. Thus effective nuclear charge increases, drawing the
electrons closer to the nucleus
iv. Exceptions of period 4 and below need not be known
2. Ionisation energy
a. Increases along the period
i. As effective nuclear charge decrease as more protons in
nucleus
ii. More energy needed to remove electron that is closer to the
nucleus
b. Except when electron is added to new sublevel
i. Shielding effect of the lower sublevel decreases effective
nuclear charge
ii. Valence electron is easier to remove due to reduced
attraction.
c. Except when first electron pair is made by adding to an unpaired
electron
i. Electron-electron repulsion within the orbital decreases
energy required to remove electron
d. To answer questions about ionisation energy,
i. Use energy level diagram
ii. Or write out the electronic configuration
3. Electron affinity
a. Decreases along the period, becoming more negative
i. Additional protons increases nuclear charge
ii. Thus more energy is released when an electron is added to
the valence orbital
b. Except when adding to an orbital with an unpaired electron
i. Electron-electron repulsion needs to be overcome when
adding the electron
ii. Thus less energy is released
c. Except when adding to a new sublevel
i. The electron is added to an orbital further away from the
nucleus
ii. Thus less energy is released.
d. Except when adding to an already half-filled sublevel
i. The half-filled sublevel is stable as all orbitals contain one
electron
ii. Energy is required to disrupt this stability, thus less energy is
released
The EA of nitrogen is positive because of this
e. Electron affinity is negative as it is the energy difference of the
electron shell from shell infinity
4. For group numbers, follow the number given in the periodic table

Electron orbitals in covalent bonds


1. Covalent bonds arises from attractive and repulsive forces
a. The atoms are most stable at a specific distance from each other
i. Bond length determined by attraction between nucleus and
electrons, and nucleus-nucleus repulsion and electronelectron repulsion
2. Lewis structure (aka dot-cross diagram)
a. Shows electrons involved in bonding as well as long pairs of
electrons
3. Valence-Shell Electron Pair Repulsion (VSEPR) theory
a. Model that minimises electron-electron repulsion by arranging
electrons are far apart as possible
b. Structure is based on number of lone pairs and bond pairs
i. Can be written with VSEPR notation: A,X and E
A is the central atom, X represents a bond pair, E is a
lone pair
Use subscript to represent multiple pairs of the same
type
c. Shape differs between electron group arrangement and molecule
shape
i. Electron group arrangement counts both lone and bonding
pairs
ii. Molecule shape removes lone pairs from the shape.
4. Valence bond theory is one way to explain covalent bonding
a. Valence bond theory explains the VSEPR structure with orbital
hybridization
i. Each electron pair (bond or lone) requires an orbital, so the
orbitals participating in the hybridization equals the number
of pairs
b. Hybridization is needed as the stable configuration of 8 electron
requires 4 pairs of electrons to be involved in bonding (or lone), and
the p sublevel can hold only 3 pairs
c. Covalent bonds are formed by the overlap of the hybridised orbitals
i. Double bonds are considered as only one bond pair when
calculating number of electrons pairs
d. Useful to show molecular shape as obtained with VSEPR theory
e. Limitations
i. Electrons are not localised in a specific region
ii. Bond energy cannot be evaluated
5. Molecular orbital theory is another way to explain covalent bonding
a. The theory does not hold the electrons within a specific orbital, but
consider them delocalised over the whole molecule
i. Uses Schrodinger equation to calculate probability of the
electron position
ii. The molecules does not have the shape described by VSEPR
b. When molecules bond, the orbitals interact
i. There is the same number of new orbitals as the number of
component orbitals
Two s orbitals interacting will produce two resultant
orbitals
ii. Only the same shell and shape of orbitals can merge

The results depends on the waves of the electrons and


their interaction
iii. The bonding orbital has a lower energy than the original
orbitals
The atoms are stabilized as electron density between
the atoms is increased
Formed when the orbitals are in-phase and
constructively interfere
iv. The anti-bonding orbital has a higher energy than the original
orbitals
The atoms are destabilized as the electron density
between the atoms is reduced, as they intensify nearer
the nucleus, facing away from the bond.
Formed when the orbitals are out-of-phase and
destructively interfere
v. A sigma bond is formed when the orbitals interact in the
same plane as the bond axis
For the first bond between atoms
vi. A pi bond is formed when there is a side to side overlap of
orbitals
For the second and higher bonds between atoms
vii. There is also electronic configuration for molecules, much like
that of atoms, which shows where the electrons are in each
mixed orbital
c. Bond order determines the stability of the molecule
i. The molecule is stable when the bond order is greater than 0
The higher the bond order, the stronger the bond
ii. When bond order = 0, the molecule is not stable
iii. Negative bond order is not possible as the electrons fill the
lower energy bonding orbitals first
d. When drawing the energy diagram
i. Optional to count the total number of valence electrons and
write the electronic configuration of the molecule
ii. First draw all the orbitals of the two atoms and label the
element for both
Note the slight energy difference between the orbitals
of different elements due to nuclear charge
The difference between p orbitals is smaller than
that between s orbitals
Draw the electrons present in the orbitals
iii. Draw the bonding and anti-bonding orbitals and label them
There should be only one pair of sigma bond orbitals,
with the rest being pi bond orbitals
For each orbital interaction, like s with s, and p
with p
The anti-bonding orbitals have a higher energy than
the bonding ones
The anti-bonding sigma bond orbitals always have
more energy than the anti-bonding pi bonds
The position of the bonding sigma bond orbitals
depends on the elements

Due to s-p orbital mixing, making the s orbitals


more stable, while destabilising the p orbital,
increasing its energy
For Boron to Nitrogen, the bonding sigma bond
orbitals are above the pi bond ones
For Oxygen and Fluorine, the bonding sigma
bond orbitals are below the pi bond ones
The presence of a less electronegative atoms
will cause s-p orbital mixing, regardless of the
presence of a more electronegative one
iv. Exception when bonding with Hydrogen
Since Hydrogen only has 1s, when bonding with Period
2 elements, it will interact with the orbital having a
close energy with it
Calculate the energy of the orbital with Bhors
equation
Usually 2s will have too little energy, so it
interacts with 2p instead
When bonding, 1s can only interact with the orbital
that is symmetrical around the bonding axis
By lectures definition, it is the 2pz orbital
The other 2 orbitals do not interact and remain
at the same energy level
Draw the bonding and anti-bonding orbital and label
Do not label with subscript since different
orbitals are interacting, just the sigma and
sigma star.
e. The molecules formed can be either paramagnetic or diamagnetic
i. Paramagnetic molecules are attracted to a magnetic field
Due to unpaired electrons in the resultant orbitals
ii. Diamagnetic molecules are repelled from a magnetic field
Due to paired electrons in the resultant orbitals
f. Useful to explain bond energy, magnetism and bond polarity

Chemical Equilibrium
1. Equilibrium reactions are dynamic, reversible and equilibrium is obtained
from either direction
2. Equilibrium constant, K
a. Ratio of activity of products over activity of reactants at equilibrium
i. Only affected by temperature
b. Based on a (activity)
i. It is the propensity for a material to contribute to a reaction
ii. It is unitless
Thus K is also unitless
iii. For pure solids, liquids and solvents, a = 1
iv. For dilute solutions, ideal gases, their activity coefficient is
approximately 1
v. Otherwise the activity is pressure or concentration
c. It indicates the ratio of products over reactants at equilibrium
i. Shows if the reaction is product or reactant favoured, or both
are equal
3. Reactant quotient, Q
a. Ratio of activity of products over activity of reactants at any time
during the reaction
i. Ratio of products and reactants will change till Q = K
When Q < K, more net products will form
When Q > K, more net reactants will form
4. Le Chateliers principle
a. States that if a system at equilibrium is disturbed, the system will
tend to shift its equilibrium position to counter the effect of the
disturbance
5. Strength of acid and bases is the inversely proportional to the strength of
their conjugate base and acid
a. Strong acids have a very weak conjugate base, allowing complete
dissociation
i. K >> 103
b. Weak acid will produce a weak conjugate base, creating an
equilibrium reaction
c. The reactivity of the acid and conjugate base are related
i. pKw = pKa + pKb
ii. pKw = 14 at 25oC
6. Amphiprotic (slightly different from amphoteric) compounds have both
acidic and basic properties and can accept or donate a proton
a. Difference with amphoteric lies with the Lewis definition based on
exchange of electrons
i. Reaction can occur where electrons are exchanged without
movement of protons
b. All amphiprotic compounds are also amphoteric
c. Zwitterions are amphiprotic as they have both negative and positive
charges
7. Polyprotic acids can donate 2 or more protons
8. Acid strength depends on several factors
a. Bond strength decreases down a group, allowing the proton to be
released more easily, as the bond requires less energy to break
i. Bond strength decrease due to increasing atomic radii
increasing bond length

b. Electronegativity increases across a period, allowing the proton to


be released more easily, as the electrons on Hydrogen are pulled
away from it
i. Electronegativity increases due to increasing effective
nuclear charge
ii. Electronegative groups also affect the dissociation of hydroxyl
groups
Quantity and quality of the electronegative groups play
a part.
9. Buffers resist changes in pH
a. Le Chateliers principle shifts the equilibrium of the acid dissociation
10.Question solving skills
a. Always write out the equation of the reaction and equation for K
i. Sometimes the inverse of K is needed for the reaction
ii. When weak acid and weak base react, sub in Ka, Kb and Kw
to find the reactions K
b. Strong acid and bases dissociate completely, thus for their reaction,
the ions can be ignored, leaving H + and OH- to react
c. Finding pH when weak acid is dissolved
i. Write out the equation
ii. Calculate the initial and final composition of the reaction
iii. Write out the K for each reaction involved
iv. Assume that the acid is weak, thus the change in initial
concentration is negligible
Always do this, or at least address this step, as it is
part of the marking
v. Calculate pH
vi. Verify assumption is plausible, as the dissociated amount is
less than 5% of the initial concentration
Else solve the quadratic equation instead using

b b24 ac
x=
2a
d. Finding pH when strong acid reacts with weak base
i. Write out the equation
ii. Calculate the initial and final composition of the reaction
iii. If equal amounts are used
pH depends on the conjugate acid
iv. If more acid than base
Assume pH depends only on the strong acid left, rather
than the weak conjugate acid
Find pH using concentration of H+ produced
v. If more base than acid
pH depends on pKa and ratio of conjugate acid and
base left
e. Finding pH when multiple acid and/ or bases are added
i. Identify the strongest base and acid from their dissociation
constant
ii. Assume all other acids and bases have a negligible effect
iii. Write the equation between the strongest acid and base
iv. Find the initial and final composition of the solution

f.

v. After the reaction between the strongest acid and bases has
occurred, assume that further dissociation is negligible and
assume the compound with the highest K determines the pH
vi. Calculate pH
Preparing buffer of certain pH
i. Choose the weak acid/base with a pKa closest to the pH
ii. Find the concentration of H+ at the target pH and calculate
ratio of conjugate and original from there.

Thermodynamics
1. Internal energy (U) is the sum of all kinetic and potential energies of all
particles in a system
a. Dependent on temperature, pressure, volume, and molar quantity
b. Path-independent
c. Only change in internal energy can be calculated, not absolute
2. There are two ways to transfer energy into a closed system.

U =w+ q

a. By doing work, w
b. Or by heating, q
c. Only in an open system does adding or removing matter changes
the internal energy
3. Work is the amount of energy flowing across the system-surroundings
boundary, accompanying a change in the volume of the system
a. It is path dependent
4. Heat is the amount of energy flowing across the system-surroundings
boundary, due to differences in temperature
a. Heat flows spontaneously from high temperature regions to low
temperature ones
b. It is path dependent
5. Enthalpy is the thermodynamic potential of the system.

H=U + pV

a. At constant pressure (and therefore volume), only the heat flow


changes the internal energy, and thus enthalpy
6. Enthalpy change in the system is taken from the surroundings:

H system= H surroudning
7. Heat capacity is the energy needed to raise the temperature of an object
by 1 K
a. At constant pressure,

q p =C p T

b. Specific heat capacity is the energy needed to raise 1 g of an object


by 1K
i.

C p =m c p

c. Molar heat capacity is the energy needed to raise 1 mole of an


object by 1K
i.

C p =n c p ,m

m stands for molar, that the c used is for molar heat


capacity instead of specific heat capacity. It does not
mean a variable is fixed
8. Standard condition fixes the pressure at 1 bar, and concentration at 1 M
a. Temperature is not fixed
b. The compound is in its most stable form at 1 bar
c. Represented by the naught superscript
9. Reference state of an element is its most stable form
a. Instead of using gaseous molecules in an equation, the elements
crystal can be used
10.The enthalpy change of formation is when 1 mole of a product is formed
from pure elements in their standard states.
a. Can be used to find the enthalpy change of reaction
11.Using Hesss Law, the enthalpy change of reaction can be found through
the addition of enthalpy changes of intermediate steps

12.Kirchhoffs Law is used to find enthalpy change of reaction at a


temperature different from given data
a. Heat capacity of products and reactants are needed
b. Else use assumption that enthalpy change is constant over a range
of temperatures
13.Take note of the different units between the data given for enthalpy,
entropy and heat capacity
14.Entropy is how much (total energy) and how widely energy (number of
possible microstates) is dispersed
a. A pure crystal only has one arrangement of atoms at 0K, thus it is
the reference point
15.Entropy changes when there is a change in state, or change in number of
moles
16.The standard entropy of a substance is the increase in entropy when it is
converted from its perfect 0K crystal, to its standard state conditions
17.Spontaneous reactions move towards equilibrium without continuous
external aid
a. Catalyst is not external aid, since it does not affect equilibrium, only
speed
18.Gibbs Free energy is the change in entropy of the universe, which by the
second law of thermodynamics, should always increase
a. Gibbs free energy is negative for spontaneous reactions as

G r =T S(universe)
b. The change in Gibbs free energy is the maximum energy available
to do work
19.Gibbs free energy under standard conditions is related to the equilibrium
constant
a. When the reaction is spontaneous,

GOr < 0 , the reaction is

product favoured, K > 1


b. When the
c. When

Gr > 0 , the reaction is reactant favoured, K < 1

GOr =0 , the reaction favours neither side, K = 1

i. Also occurs at temperature of transition.


20.Gibbs free energy is related to the reaction quotient
a. When

Gr < 0,Q< K , so the reaction occurs spontaneously to form

more products
b. When

Gr > 0,Q> K , so the reaction is spontaneous in the reverse

direction
c. When

Gr =0, Q=K , so no net change in entropy as the reaction

is in equilibrium
d. When,

Gr = Gr , Q=1 , with the

products
=1
reactants

i. Because ln(1) = 0
21.Gibbs free energy of a forward reaction is the negative of that of the
backward reaction
a.

Gforward =Gbackward

Electrochemistry
1. Two types of cells
a. Voltaic/ Galvanic cells are spontaneous and produces an electric
current
b. Electrolytic cells are non-spontaneous, using electric current for
chemical reactions
2. Similarities between the two cell types
a. Both involve redox reactions
b. Both have oxidation at the anode, and reduction at the cathode
i. Electrons flow from anode to cathode
3. Differences between the two cell types
a. The cathode in a galvanic cell is positive, while it is negative in an
electrolytic cell
i. Electrolytic cell has a negative cathode to attract the positive
ions
b. A galvanic cell requires two half cells separated by a salt bridge, an
electrolytic cells doesnt need the two electrodes to be separated
c. A galvanic cell produces a voltage equal to the cell potential
difference between the cells, an electrolytic cell requires a voltage
greater than the cell potential difference.
4. Cell notation
a. Anode electrode | Pre-oxidised form | Post-oxidised form || Prereduced form | Post-reduced form | Cathode electrode
i. Shows how electrons flow.
ii. Pre-oxidised form may be the same as electrode
5. Standard cell potential for half-cell reactions needs to include the phase
when writing the equation
6. Since half-cell potentials cannot be measured directly, the reference
electrode is they hydrogen half cell
a. Pt | H2 (1 bar) | H+ (1 M) || =

EOH

= 0V

7. Half-cell potentials shows their relative ability to act as oxidising agents


(get reduced)
a. The more positive the potential values, the more likely they are to
get reduced
8. The cell potential difference is related to the Gibbs free energy of the
reaction
a. The cell potential difference has to be positive for the reaction to be
spontaneous, else the reaction will happen in the opposite direction
9. The cell potential difference at any point during the reaction can be found
using the NERNST equation

Kinetics
2. Reaction rate is the change in concentration of reactants/ products per
unit time
a. Product concentration will increase, while reactant will decrease
over time until equilibrium
b.

1
[ A]
a
Rate of reaction=
t
A

i. Where

is the reactant, and

is the stoichiometric

ratio of

ii. Negative since the concentration of

is decreasing

iii. Unit is concentration over time


1

Ms

mol L1 s1

c. Rate of reaction is determined from experimental data


i. Such as change in light absorption amount by reaction vessel
ii. Such as change in conductivity if ionic products are formed
iii. Such as change in pressure if gaseous compounds are
involved
3. Rate Law is an equation that shows the dependence of the reaction rate
on the concentration of each reactant
a.

Rate=k [ A ] [ B ]
i.

is the rate constant and is only affected by temperature

(and catalyst)

is not affected by catalyst if catalyst concentration

is included in the rate law equation


Unit depends on the order of reaction
1 1

Zero order is

mol L s

First order is

s1
L mol1 s1

Second order is
Third order is

ii.

2 1

L mol s

Remember to use the correct units for


and

are the order with respect to the reactant

b. The order with respect to the reactant is determined experimentally


i. It is independent of the stoichiometry of the reactions
ii. Done by changing the initial concentrations of reactants and
measuring the initial rate
4. To find reactant at time

t , with known

(or vice-versa) and final and

initial concentrations, from integrated rate law


a. For zero order reaction with respect to the reactant

[ A ] t=kt + [ A ] 0

i.

Thus

k=

is the slope,

[ A ] 1[ A ] 0
t 1t 0

b. For first order reaction with respect to the reactant

ln (

i.

[ A ]t
)=kt
[ A ]0

Convert known concentrations to

ln [ A ] t=kt + ln [ A ]0

ii.

Thus

for

y=mx +c

graph

k=

is the slope,

ln [ A]

ln [ A ] 1ln [ A ] 0
t 1t 0

c. For second order reaction with respect to the reactant

1
1
=kt+
[ A ]t
[ A ]0

i.

Thus

Plotting a graph of

is the slope,

1
1

[ A ]1 [ A ]0
k=
t 1t 0

ln [ A]

against

will not give a

straight line
d. Unknown order of reaction can be tested by putting in known

and

to see which equation fits

i. Or plot the graphs to see which kind of

and

gives a

straight line
e. The equations apply only to reactants, since initial concentration of
product is 0
i. Find product concentration by first finding reactants
5. Half-life is the time required for the reactant concentrations to drop to half
of its initial value
a. Substitute

[ A ]1=
2

t1

(which is

[ A ]0
2

into the integrated rate law equation to find

b. For zero order reaction


i.

t1 =
2

[ A ]0
2k

c. For first order reaction


i.

t 1 =ln
2

2
k

The half-life is independent of the initial reactant


concentration

Each half-life measured from any reactant


concentration is an equal period of time
Thus different first order reactions with the same

gives the same half life

d. For second order reaction


i.

t1 =
2

1
k [ A ]0

Each half-life depends on the initial reactant


concentration
Thus each half-life is twice as long as the preceding
one
6. Reaction mechanism is a sequence of reaction steps that describes the
pathway from reactants to products
a. An elementary reaction is a reaction where reactants react directly
to form the products in a single reaction step with a single transition
state
i. Each reaction step is an elementary reaction
b. The rate law for elementary reaction follows its molecularity
i. Molecularity classifies elementary reactions based on the
number of molecules on the reactant side of the equation
c. The rate determining step is the slowest step in the reaction
mechanism as it limits the rate of the entire reaction
i. The overall reactions rate equation follows the molecularity
of the slow step
7. Catalyst is a substance that increases the rate of reaction without itself
being consumed at the end of the reaction
a. It is used in one step and regenerated in another.
b. The concentration of catalyst can be included in the rate law
equation too

Organic Chemistry
Nomenclature
1. Find the parent chain
a. The longest carbon chain that contains the functional group
2. Start numbering the carbons from the end that gives the lowest first
functional group or substituent number
a. Lowest first functional group takes priority.
b. In cycloalkane, make the carbon-carbon double bonds between
carbon 1 and 2
c. Compare second substituent number only if the first one is tied from
both directions
d. If all the substituents can receive the same number, number by
alphabetical priority
3. Name substituents in alphabetical order with their locant
a. Prefixes indicating identical group quantity is not considered
4. Use comma to separate numbers, dashes to separate branches, and
brackets when there is secondary branching
a. No dash between branch and parent at the end
5. Prefixes
a. Functional groups
i. Cyclo-___-ane
ii. Cyclo-___-yl
iii. Phenyl
When benzene is a substituent
iv. Nitro
-NO2
v. a
b. Numbers
i. Methii. Ethiii. Propiv. Butv. Pentvi. Hexvii. Heptviii. Oct
ix. Nonx. Decxi. Undecxii. Dodecxiii. Tridecxiv. Tetradecxv. Add an a, when there are 2 or more substituents. For
example,
Metha Buta Tridecaxvi. But not for alcohols since the substituent numbers are added
after the ane
Hexane-1,4-diol
6. Suffix

a. Alkane
i. ane
b. Alkane branch
i. yl
c. Alkene
i. ene
d. Alkene branch
i. enyl
e. Alkyne
i. yne
f. Alkynes branch
i. ynyl
g. Alcohol
i. anol
ii. ane-X,X-diol
There is an e if more than one alcohol group
h. Alcohol alkene
i. X-en-X-ol
i. Ether
i. ___-yl ____-yl ether
j. Ether as substituent
i. oxy
k. Aldehyde
i. anal
l. Ketone
i. an-X-one
ii. ane-X,X-dione
m. Ketone alkene
i. X-en-X-one
n. Ketone as substituent
i. oyl
o. Carboxylic acid
i. anoic acid
ii. anedioic acid
Since the acid function group must be at the terminals
p. Carboxylic acid in a cyclo___
i. carboxylic acid
Like cyclopent-1-enecarboxylic acid
q. Nitrile
i. -anenitrile

General formula
1. Alkane parent chain
a.

Cn H 2 n+2

2. Alkane branch
a.

Cn H 2 n+1

3. Cycloalkane
a.
4. Alkene
a.

Cn H 2 n
Cn H 2 n

5. Alkyne
a.

Cn H 2 n2

6. Benzene

Drawing organic molecules


1. Newman projection
a. Two carbon atoms are aligned and viewed end-on
i. Carbon atoms represented by a dot and circle
R-groups attached to the first carbon are joined to the
dot
R-groups attached to the second carbon are joined to
the circle
b. All R groups are shown with spatial orientation
i. As in the direction of bond matters
ii. Torsional strain can be shown
Staggered projection where all bonds are evenly
spaced out
Eclipsed projection where all bond are overlapping
Thus the rotation is not perfectly free
iii. Steric strain can be shown
When two bulky groups are 60 degrees to each other
(Gauche conformation) instead of being 180 degrees
apart (anti conformation)
2. Sawhorse
a. Shows a carbon-carbon bond from an angle
b. All R groups are shown with spatial orientation
c. Chair conformation for cyclohexane
i. Draw two parallel lines
ii. Have a carbon situated at of the distance between the
lines at both sides
iii. Join all the six carbons together in a ring
iv. Fill in the 6 equatorial hydrogen atoms
4 by following the zig-zag lines
2 by drawing lines parallel to the original two lines at
the middle carbons
v. Fill in the 6 axial hydrogen atoms
3 above the plane to make a triangle formation
3 below the plane to make a triangle formation
d. Ring flip can occur for cyclohexane
i. Draw the chair conformation with the parallel lines facing a
mirrored direction
ii. Carbon 1 goes from bottom left to top left
iii. Carbon 4 goes from top right to bottom right
iv. All the equatorial and axial R-group swap orientation.

Reactions
1. Alkanes
a. Combustion with oxygen
i. Uses oxygen and heat
ii. Produces carbon dioxide and water
b. Halogenation

i. Uses halogen and UV light


ii. Free-radical substitution occurs
Initiation
Propagation
Termination
iii. Mixture of halogenated products are formed
2. Alkenes
a. Electrophilic addition of water
i. Uses H+/H2O and organic solvent (ether) to dissolve organic
compound
ii. Carbocation is formed on the carbon with more substituents,
after addition of one hydrogen atom
Due to hyperconjugation stabilising the charge
This is Markovnikovs rule
iii. Hydride shift can occur to form a more stable carbocation
Note that there is no quaternary carbocation
iv. Nucleophile, H2O, is then added to the carboncation to give
-OH
b. Electrophilic addition of hydrogen halide
i. Uses HF and organic solvent (ether) to dissolve organic
compound
ii. Similar to above, but nucleophile is halogen to give X
c. Electrophilic addition of halogen
i. Uses X2 and organic solvent (ether) to dissolve organic
compound
ii. The halogen approaches the double bond and undergoes
induced polarisation
iii. Halogen bonds breaks, giving a halogen ion, and a halogen
with a positive charge bound to both carbons
Forms a 3-membered ring, that has high ring strain and
is unstable
iv. Nucleophile, X-, attacks the electrophile joined to the carbons,
X+
Nucleophile is added to the carbon that is more stable
with a partial positive charge
d. Electrophilic addition of hypohalous acid
i. Uses X2 and H2O, to give HOX, and organic solvent (ether) to
dissolve organic compound
ii. Similar to above, where X+ is the electrophile that joins to
both carbons
iii. While OH- is the nucleophile
e. Electrophilic addition of Hg(OAc)2
i. Uses Hg(OAc)2/H2O, and organic solvent (ether) to dissolve
organic compound
ii. Similar to above, but with HgOAc+ as electrophile that binds
to both carbon
iii. OH- is the nucleophile
f. Electrophilic addition of BH3
i. Uses BH3 and organic solvent (ether) to dissolve organic
compound
ii. H-BH2 approaches the double bond from the same plane
It is orientated to avoid steric hindrance of BH2

Follows anti-Markovnikovs rule


Since Hydrogen is added to the carbon with
more substituents, to avoid steric hindrance
g. Electrophilic addition of hydrogen
i. Uses H2, PtO2 catalyst and organic solvent (CH3COOH) to
dissolve organic compound
Or Pd/C and CH2CH2OH
ii. The hydrogen molecule is adsorbed onto the catalyst,
allowing it to attack the alkene from the same plane
h. Reduction of R-groups to produce alcohol
i. -HgOAc can be reduced by NaBH4, to give OH
ii. BH2 can be reduced by H2O2/OH- to give OH
i. 2 step addition of diol
i. Using mCPBA and CH2Cl2 as solvent
Gives epoxide, where an oxygen is bonded to both
carbons
Use H3O+/H2O to add OH to both carbons
ii. Using OsO4 and Pyridine as solvent
Gives cyclic osmate intermediate
Use NaHSO3 and H2O to add OH to both carbons
j. Oxidation reaction to split the bond
i. Use O3 to give ozonide
ii. Use Zn and H3O+ to add double-bond O to both carbons
3. Cycloalkenes
a. Similar to alkenes but there is anti- and syn-addition
i. All reactions that involve electrophiles and nucleophile will be
anti-addition
Since nucleophile will attack from the opposite plane
ii. Hydroboration (H-BH2) and hryogenation will be syn-addition,
since they approach from the same plane
b. Subsequent reduction would give the syn- or anti-addition of water,
and on different carbons
c. mCPBA gives anti-addition as it is a two step reaction
d. OsO4 gives syn-addition as it is a one step reaction
4. Alkynes
a. Electrophilic addition similar to alkenes
i. Turns the triple bond into a double bond
ii. Can undergo an further reaction to give single bond
b. Nucleophilic substitution to add carbons
i. Use terminal alkyne and strong base (NaNH 2) to produce
acetylide anion and cation (salt)
ii. Add Halogenoalkane that contains the desired carbon chain
Halogen reacts with nucleophile (anion) and transfers
the carbon chain to the alkyne
The triple bond is still preserved
5. Benzene
a. Electrophilic substitution of halogen (Halogenation)
i. Uses X2/FeBr3
The X2 reacts with FeBr3 to produce an electrophile, X+
The electrophile attacks the double bond, causing a
carbocation
This is stabilised by resonance

Re-aromatization occurs to eject the hydrogen, keeping


the halogen
b. Electrophilic substitution of halogenoalkane (Friedel-Crafts
Alkylation)
i. Uses halogenoalkane and AlCl3
The halogenoalkane reacts with AlCl3 to produce an
electrophile
Acyl cation is stabilised by resonance
Take note of hydride shift
Attack is similar to above
ii. As alkyl is an activating group, it causes further alkylation
iii. Does not occur if a strong electron-withdrawing group is
present
c. Electrophilic substitution of nitrogen dioxide (Nitration)
i. Uses concentrated HNO3/H2SO4
The reacts HNO3 with H2SO4 to produce NO2+
Attack is similar to above
d. Electrophilic substitution of SO3H (sulfonation)
i. Uses fuming H2SO4 (fuming means contains SO3)
The reacts SO3 with H2SO4 to produce SO3H+
Attack is similar to above
e. Oxidation of alkyl substituent
i. Uses KMnO4, H2O and heat OR Na2CrO7, H2SO4/H2O and heat
Requires the first carbon to not be quaternary as
hydrogen is needed
ii. Converts the alkyl chain into COOH
f. Hydrogenation of benzene requires a highly effective catalyst
i. Uses H2, Rh/C, ethanol at 1 atm and 25 degrees Celsius
Syn-addition of hydrogen
6. Halogenoalkane
a. Elimination of hydrogen halide
i. Uses KOH and organic solvent
ii. Gives alkene, KX and water
X goes to K, H goes to OH.
7. Alcohol
a. Elimination of water
i. Uses H2SO4, H2O and THF (organic solvent) at 50 degrees
Celsius
ii. Gives alkene and water
8. Step up reactions
a. Terminal alkynes through 2-step
i. Use strong base to give salt
NaNH2/NH3
ii. Use RX, where R is the desired carbon chain
iii. The triple bond is still intact
b. Friedel-Craft Alkylation
i. Only for benzene through electrophilic substitution
ii. Use RX and FeBr3
c. Friedel-Craft Acylation
i. Only for benzene through electrophilic substitution
ii. Use RCOX and FeBr3
iii. Forms a ketone

d. Grignard Reagent with carbonyl compound (nucleophilic addition)


i. R from R-Mg-X gets added to the R-CR=O, forming R-CRROH
e. SN2 or SN1 with nucleophile containing R
i. Make nucleophile strong
Make OH strong by reacting with NaH to produce salt
that has negative charge
9. Quick reference reagents
a. Alkene and Alkyne
i. H3O+ + H2O
Electrophilic addition of water (carbocation)
ii. HX
Electrophilic addition of HX (carbocation)
iii. X2 +H2O (excess)
Electrophilic addition of HOX (three-membered ring)
iv. X2
Electrophilic addition of X2 (three-membered ring)
v. Hg(OAc)2 + H2O + NaBH4
Electrophilic anti-addition of H & OH (three-membered
ring)
vi. BH3 + H2O2,OH Electrophilic syn-addition of H & OH (parallel)
vii. H2,Pd
Electrophilic syn-addition of H2 (parallel)
viii. mCPBA + H3O+ +H2O
Electrophilic anti-addition of OH & OH (threemembered ring)
ix. OsO4 + NaHSO3
Electrophilic syn-addition of OH & OH (parallel)
x. O3 + Zn,H3O+
Breaking double bond into ketone/aldehyde
xi. NaNH2,NH3 + RX
For alkyne, substitution with R
Step up reaction
xii. NBS, uv
Bromination of allylic position (note free radical shift)
b. Benzene
i. X2,FeBr3
Electrophilic substitution with X (halogenation)
ii. Concentrated HNO3, concentrated H2SO4
Electrophilic substitution with NO2 (nitration)
iii. Fuming H2SO4
Electrophilic substitution with SO3H (sulfonation)
iv. RX,FeBr3
Electrophilic substitution with R (Friedel-Crafts
alkylation)
v. RCOX,FeBr3
Electrophilic substitution with RCO (Friedel-Crafts
acylation)
vi. KMnO4 + H3O+
Oxidation of alky substitute (not tertiary) into COOH

vii. H2, Rh on C
Electrophilic addition of H2 to convert benzene to
cycloalkane
c. Alkyl halides
i. Mg, THF
Produces Grignard Reagent
Reacts with weak acid (H2O, ROH. RCO2H, RNH2) to
give alkane
Forms a salt with the acid as by-product
Reacts with carbonyl compounds to give alcohol in a
step up reaction
Reacts with dry ice to give carboxylic acid (in ion form)
ii. Nucleophile with lone pair of electrons
SN2 reaction
SN1 reaction
E2 reaction
E1 reaction
d. Alcohol
i. Nucleophile for tertiary alcohol only
SN1 reaction
Use HX to produce alkyl halide
ii. SOCl2
SN2 Reaction for primary and secondary alcohol to
produce alkyl chloride
iii. PBr3
SN2 Reaction for primary and secondary alcohol to
produce alkyl bromide
iv. TosCl
To make better leaving group for SN2, SN1, E2, E1
v. Grignard Reagent
Gives H to R in R-Mg-X, while making a salt
vi. H3O+, THF
Acid-catalysed dehydration to give alkene
More stable alkene is the major product
vii. Carboxylic acid or acid halide
Forms ester
viii. Dess-Martin periodinane
Oxidises primary alcohol to aldehyde only
ix. CrO3 + H3O+
Oxidises primary alcohol to carboxylic acid
Oxidises secondary alcohol to ketone
x. K2Cr2O7 + H3O+
Oxidises primary alcohol to carboxylic acid
Oxidises secondary alcohol to ketone
xi. NaH,THF + RX
Forms ether (R-O-R)
e. Ester
i. Grignard Reagent + H3O+
Removes previous alcohol R, and replace with 2 R
from 2 R-Mg-X, while producing a tertiary alcohol

Thus two Grignard Reagent is needed for every


one ester
By-product is the ROH, the original alcohol that
formed the ester
ii. LiAlH4 + H3O+
Reduction to give acid and alcohol, but the acid is
further reduced to alcohol
iii. DIBAH + H3O+
Reduction to give acid and alcohol, but the acid is
further reduced to aldehyde
f. Thiols
i. Br2 or I2 (H2O2 in cells)
Oxidised to yield disulfides (RSSR)
By-product is HX
Reversed with Zn, H3O+ (FADH2 in cells)
ii. NaH,THF + RX
Forms sulphide (R-S-R), faster rate than ether
formation in alcohol
g. Sulphide
i. H2O2 + H2O
Oxidised to form sulphoxide (R2SO)
Further oxidation with CH3CO3H gives sulphone
(R2SO2)
h. Carbonyl compounds
i. NaBH4 + H3O+
Reduces aldehydes and ketones to alcohol
ii. LiAlH4 + H3O+
Reduces aldehydes and ketones to alcohol
Also strong enough for acids and ester
iii. Grignard Reagent + H3O+
Nucleophilic addition forms an alcohol while stepping
up by the R in R-Mg-X
iv. CrO3+ H3O+
Oxidise aldehyde to carboxylic acid
v. RNH2
The C=O becomes C=N-R
By-product is water
vi. H2O, H3O+
Acid-catalysed hydration to give diol
vii. H2O, OH Base-catalysed hydration to give diol
viii. ROH, H3O+
Acid-catalysed nucleophilic addition to give acetals
[R2C(OR)2]
Two units of alcohol for each unit of carbonyl
i. Carboxylic acids
i. ROH
Esterification
Step up reaction
j. Nitrile
i. OH-, H2O

Base-catalysed hydrolysis to give an amide (in ion


form) first, further hydrolysis to give carboxylic acid (in
ion form)
ii. H3O+, H2O
Acid-catalysed hydrolysis to give an amide first, further
hydrolysis to give carboxylic acid
iii. LiAlH4
Forms amine
iv. Grignard Reagent + H2O
Forms an imine anion that hydrolyses to ketone

Alkanes
1. Alkanes are saturated hydrocarbons consisting of only carbon and
hydrogen
a. Each carbon is sp3 hybridised, forming a bond angle of 120 degrees
2. Normal alkanes are unbranched
3. Isomers are compounds with the same molecular formula, but different
structures
a. Different structures like presence and location of branching
4. The degree of a carbon depends on how many other carbons it is attached
to
a. Primary carbon is only bonded to one other carbon, with the other 3
bonds being attached to Hydrogen or other elements
b. Secondary carbon is bonded to 2 other carbons. Tertiary to 3,
quaternary to 4.
5. Cycloalkanes are aliphatic cyclic hydrocarbons
a. They are saturated non-benzene rings
6. Melting and boiling point increases with molecular weight due to greater
London forces
a. The shape of the molecule also affects surface area for
intermolecular forces
b. Relatively low compared to other organics as VDW forces are easily
broken

Cycloalkanes
1. Cycloalkanes are aliphatic cyclic hydrocarbons
a. They are saturated non-benzene rings
b. There is no free rotation around the carbon-carbon bond without
breaking the ring
i. This allows for cis-trans isomerism
2. There are angle strains in cycloalkanes, as bonds are forced into an angle
differing from the 120 degrees expected from an sp 3 hybridised carbon
a. Greater in small rings (up till 5) that have little flexibility
3. There are three types on strains present in cycloalkanes
a. Angle strain
i. Due to expansion or compression of bond angles
b. Torsional strain
i. Due to eclipsing, adjacent bonds
c. Steric strain
i. Due to repulsion of atoms in close proximity
d. Cyclopropane has the greatest strain, followed by cyclobutane and
cyclopentane

i. Angle strain decreases as deviation is reduced, but torsional


strain varies
ii. Cyclopentane has the least torsional strain due to non-planar
arrangement
One carbon rises above the plain
e. Cyclohexane has no strain due to chair conformation which is
conformationally mobile
i. No angle strain as bond angle is 111.5 degrees
ii. No torsional strain as carbon-hydrogen bonds are staggered
iii. No steric strain, as substitutes are hydrogen that have small
electron clouds
iv. Ring flip can occur to change the axial and equatorial Rgroups
4. Substituted cyclohexane experiences 1,3-diaxial steric interactions when
the substituted R-group is in the axial position
a. Steric strain between the 3 R-groups in the same plane
i. Total steric strain equals twice the energy of the 1,3-diaxial
steric interaction
b. Can be avoided by ring flip so that the bulkier R-group faces
outwards into empty space
5. Polycyclic molecules cannot undergo ring flip, as the fused rings are rigid

Alkenes
1. Alkenes are unsaturated hydrocarbons that contain at least one carboncarbon double bond
2. Alkenes that are more substituted are more stable than those less
substituted
a. Due to hyperconjugation, where there is interaction between the pi
carbon-carbon double bond, and the sigma carbon-hydrogen bonds
on adjacent atoms.

Alkynes
1. Alkynes are unsaturated hydrocarbons that contain at least one carboncarbon triple bond
2. Terminal alkynes are slightly acidic, and can react with strong bases
(NaNH2)
a. Terminal hydrogen is removed to form an acetylide anion

Benzene
1. Benzene is a cyclohexa-1,3,5-triene, with all the 6 pi electrons delocalised
into an electron ring around both sides of the plane.
a. The molecule is planar as all carbons are sp 2 hybridised
b. The delocalisation makes the benzene stable
i. Thus less reactive and does not undergo electrophilic addition
2. Inductive effects are the withdrawing of electrons towards a pi bond
3. Resonance effects are the movements of electrons that shift a charge
around by bond formation and breaking
a. Positive charge is most stabilised on a nitrogen atom, followed by
oxygen, then the halogens
i. Since they have a lone pair to form a bond, to shift the
charge

ii. Stabilisation decreases since they increase in


electronegativity
4. Arenes are alkyl-substituted benzenes
5. Positions of di- or multi-substituted benzene can be named
a. Ortho- is at the relative 2nd carbon
b. Meta- is at the relative 3rd carbon
c. Para- is at the relative 4th carbon
6. Reactivity is determined by substituted groups
a. Electron-donating groups increase reactivity
i. By induction of alkyl substituent through hyperconjugation
2,4 directing
ii. By resonance with electronegative atoms directly connected
There is a lesser inductive effect that withdraws
electrons
2,4 directing
b. Electron-withdrawing groups decrease reactivity
i. By halogens due to inductive effect
2,4 directing due to resonance effect
ii. By electronegative groups not directly connected to benzene
3 directing
iii. By positive charges
Little chance of further reaction

Isomerism
1. Structural isomers have their atoms connected in a different order while
having the same molecular formula
a. Branching
2. Stereoisomers have their atoms connected in the same order, but different
3D geometry
a. Cis-trans isomerism
i. Requires an identical R-group at both sides of the bond
ii. If the R-group are at the same side it is cis-, else it is transiii. Cis- isomers are less stable than trans- isomers due to steric
strain
b. E,Z isomerism
i. Requires two R-groups with different weight at each side of
the bond on both sides
Weight is determined by Cahn-Ingold-Prelog sequence
rules
Take the atomic number of the first atom
connected to the carbon
Only consider the next atom if they are tied
Treat double bonds as if bonded to two of the
same atom
ii. If the high weighted R-group is on the same side, it is (Z)-,
else (E)iii. Add a number before the letter if there is more than one
restricted rotation available
(2Z,4Z,6E,8Z)-undeca-2,4,6,8-tetraene

Halo alkanes

1. SN2 reaction (second order) has inversion of stereochemistry.


a. Low steric hinderance in substrate
b. Strong nucleophile with lone pair of electons
i. Nucleophilicity parallels basicity
ii. Nucleophilicity increases down a column
iii. Nucleophilicity is greater on a negatively charged ion than
neutral one
c. Leaving group that stabilises the negative charge
i. Leaving group cannot be OH-, NH2-, OR They are strong bases and will attack the carbon again
Thus unlikely to break from carbon
Exception for alcohol with PBr3 or SOCl2 since they
activate the -OH
ii. TosO- is the best leaving group, so use TosCl to form TosO
d. Aprotic solvent
i. Protic solvents would form a cage around the attacking
nucleophile
2. SN1 reaction (first order) produces a partial racemic mixture due to steric
hindrance
a. Substrate that can stabilise the carbocation
b. Nucleophile has no effect
c. Leaving group should be weak base like SN2
i. Leaving group cannot be OH-, NH2-, OR They are strong bases and will attack the carbon again
Thus unlikely to break from carbon
ii. TosO- is the best leaving group, so use TosCl to form TosO
d. Protic solvent
i. They stabilise the carbocation by forming a cage around it
Carbocation solvation
3. Elimination reactions usually give a mixture of alkene products
a. Zaitsevs rule states that the more highly substituted alkene is the
major product
i. Due to hyperconjucation stabilising the alkene
b. Nucleophiles are also bases, so either SN or E can occur
4. E2 (second order) needs a strong base to attack the acidic hydrogen on
the carbon beside the one with the halogen
a. Substrate should be highly substituted to form a more substituted
alkene
i. No steric hindrance unlike SN2
ii. Thus more bulky substituents will favour E2 over SN2
b. A strong nucleophile is a strong base
c. Leaving group should be weak base like SN2
d. Anti-elimination occurs giving only one stereoisomer product
i. For cycloalkane, the leaving group and acidic hydrogen needs
to be trans diaxial
As in they are in axial position on opposite sides of the
plane
If one is in equatorial, it cannot occur
e. Solvent is not as important
5. E1 (first order) similar to SN1
a. Substrate should be more substituted to from more stable
carbocation

b. Nucleophile does not affect reaction since it is not in the rate


limiting step
c. Leaving group should be weak base like SN2
d. Solvent should be protic to solvate the carbocation
e. Halogenoalkane will give roughly equal proportions of E1 and SN1
products

Alcohol
1. Alcohols, phenols and ethers are organic derivatives of water
a. R-OH is alcohol
b. Ar-OH is phenol
c. R-O-R is ether
2. Thiols and sulphides are sulphur analogues of alcohol and esters
a. R-SH is thiol
b. R-S-R is sulphide
3. Alcohol has higher boiling points than thiols since sulphur does not form
hydrogen bonds
4. Alcohols are both weakly basic and weakly acidic like water
a. Dont react with weak bases (HCO3, RNH2), slightly with metal
hydroxides (OH-), fully with alkali metals and strong bases (NaH,
NaNH2)
b. Reacts will with Grignard Reagent from alkyl halides, to add
hydrogen to the reagent
i. Alcohol itself forms a salt with MgX
5. Thiols produced from adding SH- nucleophile in SN2 reaction with alkyl
halide