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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
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
( )
( )
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
+
H
lg
conjugate base
acid
b. pH =
p K a+ lg
c. pH =
p K w pOH
U =w+ q
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:
Cp=
q
T
H r = vi H f ,i ( products) v i H f ,i (reactants)
i
a.
vi
13.Kirchhoffs Law:
H or ( T ' ) = H or ( T )+ C op ,r (T ' T )
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 =
H Otrans
T trans
Strans =S surrounding
S surr=
H Or
T surr
Gr = H r T S r
Gr = vi G f ,i ( products) v i Gf ,i (reactants)
b. From formation:
Gr =Gr + RT lnQ
i. R = 8.315 J/K.mol
Gr =0 :
d. At equilibrium, Q = K,
GOr =RT ln K
Gr =nF Ecell
Gforward = Gbackward
G Or
Hr
T transition =
O
Sr
changes sign
O
cell
E =Ecathode E anode
Ecell =Ecell
RT
ln Q
nF
[ 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
Ea
temperature, and
rate=
[A] =
k reactant fwd
k reactant bwd
formation of
k reactant fwd n
[ B]
k reactant bwd
if the
[ 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
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 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
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
C p =m c p
C p =n c p ,m
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,
more products
b. When
direction
c. When
is in equilibrium
d. When,
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
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 stoichiometric
ratio of
is decreasing
Ms
mol L1 s1
Rate=k [ A ] [ B ]
i.
(and catalyst)
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
t , with known
[ A ] t=kt + [ A ] 0
i.
Thus
k=
is the slope,
[ A ] 1[ A ] 0
t 1t 0
ln (
i.
[ A ]t
)=kt
[ A ]0
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
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
straight line
d. Unknown order of reaction can be tested by putting in known
and
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
t1 =
2
[ A ]0
2k
t 1 =ln
2
2
k
t1 =
2
1
k [ A ]0
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
Reactions
1. Alkanes
a. Combustion with oxygen
i. Uses oxygen and heat
ii. Produces carbon dioxide and water
b. Halogenation
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
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
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
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
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