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General:
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Gases Ideality:
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When there are more than 2 gases, and its a mixing scenario given,
ALWAYS find individual partial pressures and then add up to find total
pressure. Dont just add or use proportion.
At higher temperature, same gas and no.of mol will deviate less from
ideality because the molecules possess higher average KE more able to
overcome inter-molecular forces of attraction.
Equilibria:
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Chemical Energetics:
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Entropy gives the measure of the degree of extent to which particles and
energies are distributed within a system.
Increase in Temperature Rise in average KE of particles more ways to
distribute energy increase in entropy.
When a solution ( containing a solute ) becomes more diluted, entropy
increases.
When given a Temp-time graph, and asked to find max temp change of a
reaction. Here are the steps: Measure the receding (cooling) gradient,
extend backwards until the instant (time) when the mixture is added.
A negative deltaG value and large Kc value means the the reaction in
the forward reaction is spontaneous will go to completion.
Which compound releases most energy on combustion? The most
oxidized compound will be least exothermic because it will contain more
O atoms -> because bonds involving O are usually stronger, so RBBT is
higher. So, less energy given out.
Reaction Kinetics:
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Organic Chemistry:
General:
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Alkanes:
Alkenes:
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If an alkene is fixed into a ring ( cyclo compound ), the C=C double bond
does not cause geometric isomerism.
Arenes:
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Carbonyl compounds:
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Carboxylic Acids:
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Acid chlorides are very acidic they dissociate to give HCL. They are
even more acidic than the corresponding carboxylic acid.
A cyclic compound with C-C single bond can exhibit cis-trans
isomerism because if the bond is pointing into the ring/outside
the ring is different; cuz you cannot rotate about the ring so it is
not the same.
Amides are neutal compounds.
If PCl5 is there in the reactant but Cl is not in the product, it must have
formed an acid chloride which then formed an amide, thus, losing the Cl.
Halogen derivatives:
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Compounds with C-F bond usually chemically inert cuz C-F bond energy
very large.
Excess NH3 needs to be added to halogenoalkane to increase the
chance of the alkyl halide reacting with the NH3 rather than the amines
already formed. This prevents forming of secondary amines and so on.
Why is chlorobenzene inert ? The p orbital on the Cl atom overlaps
with the pi orbitals of the benzene. Hence, lone pair is delocalized into the
benzene ring by resonance. This results in C-Cl bond having partial double
bond character and hence, harder to cleave. Thus, chlorobenzene inert
towards nucleophilic sub.
The by-product of the base hydrolysis of nitriles is ammonia.
For Organic compounds containing halogens attached to C atoms. If it
undergoes alkaline hydrolysis ( NaOH ), all the Cl atoms are converted to
OH by Nucleophilic substitution.
In a halogenoalkene, in a C-X bond , if the same C is involved in a C=C
bond, then the electrons from the X atom is delocalised into the pie C=C
bond, strengthening the C-X bond, so making it unreactive. Pie orbital
overlap.
LiAlH4 is very reactive so it must be kept dry ( dry ether ) and there is no
need for heating or reaction may become too vigorous. Moreover, H2 with
Ni/Pt should not be used to reduce COOH as it does not happen easily.
LiAlH4 in dry ether is the best option for COOH. It can also reduce esters
(hydrolysis then COOH -OH) and amides ( similar way ) but cannot
reduce C=C.
If you want to oxidize an aldehyde to ketone which is on a sidechain of a
benzene ring, do not use KMnO4 as that will lead to complete oxidation
and give benzoic acid instead.
Whether complete side chain oxidation occurs or not, depends on the first
carbon atom attached to the benzene ring. If the first carbon, is a
tertiary carbon ( attached to 4 c atoms ) then complete side chain
oxidation does not occur.
The no. of mol of CO2 given out from the complete oxidation of side chain
in benzene is calculated by totally how many mole of C atoms is lost
when each side chain is oxidised to COOH.
Reduction has NO effect on ester linkages
When KMnO4 is used as an oxidising agent in alkaline medium, the
solution first changes to dark green ( MnO4 2- ions) and then brown ppt is
seen (MnO2). In acidic medium, changes from purple to colourless
(Mn2+)
Once C6H5NO2 is reduced to C6H5NH2, it cannot be oxidized back.
Distinguishing Tests:
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Nitrogen Compounds:
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Chemical Bonding:
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When Fluorine is the central atom, F cant form dative bonds because it is
very electronegative.
When question says why a compound can exist with Cl but not with F, a
possible reason could be that Cl is a period 3 element and can expand its
octet to accommodate more electrons.
In an ionic lattice structure, each cation is surrounded by all anions. Each
anion is surrounded by all cations.
When considering bond length, (especially between carbon atoms), look at
the SP hybridisation. If one of the C atoms is SP1 hybridised, then it has
more significant S character and will make the bond stronger bond
length smaller.
A co-ordinate ( dative ) bond is a covalent bond and if its the first pair of
bonding electron between two atoms, it is also a sigma bond.
If a compound, got functional groups containing O and H closeby each
other, then it is likely to have INTRAmolecular hydrogen bonds. More
intramolecular H bonding less INTERmolecular bonding lower
Melting point.
Atomic structure:
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Periodicity:
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Transition elements:
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When copper ions and iodide ions are involved, and a brown ppt is
formed. It is a white ppt of CuI and is brown because it is in brown Iodine.
SiCl4 cant be used to produce high charge density cations in water as it
will hydrolyse to give SiO2 and HCl. High charge density ions have high
polarising power. They weaken the O-H bonds in water molecules to
release H+ ions. Acid base reaction then can occur with other compounds.
The main definition of T.E: They have partially filled D-orbitals.
When water is added to a solution containing a transition element complex
ion, it does now always need to be Ligand Exhange; can just cause a shift
in equilibrium if water is part of a reaction in the previous step.
Sometimes, you might need to investigate the entropy of different
complex ions. In this case, you write out the equation of formation of the
ions. i.e; from the central ion + 6 water ligands + the reacting ligand to
form the new product. See the total number of molecules before and after
and observe entropy change.
For example:
Let en represent H2NCH2CH2NH2
[Ni(H2O)6]2+(aq) + 6NH3(aq)
[Ni(NH3)6]2+(aq) + 6H2O(l)
7 particles
7 particles
[Ni(H2O)6]2+(aq) + 3en(aq)
[Ni(en)3]2+(aq) + 6H2O(l)
4 particles
7 particles
To form [Ni(en)3]2+(aq), three en molecules replace 6 water
molecules, hence S is more positive.
If the question gives you the colour of the complex, and asks you about
the energy gap in the complex, to compare the wavelengths, you should
compare the wavelength of the complement of its colour ( because
you want the color THAT IS ABSORBED )
When trying to find the co-ordination number of an ion, you should know
the dentatity ( type of ligand ) first. i.e: so if bidentate ligand, if ratio of
ligand to central ion is 2:1 then co-ordination number is 4.
When asks about presence of dipoles, you must answer based on the
structure and shape of the complex ion to see if the dipoles cancel
each other or not.
Transition metals are the only metals which give coloured ions in
aqueous solutions.
Phenols and all its derivatives are acidic.
When colour change occurs in the complex ion of transition
element, its because: in the presence of ligands, the energy gap
between the d-orbitals change. So, different ligands lead to
different energy gap so different region of visible light spectrum
absorbed so different colour.
Usually, if need to remove excess OH- ions in solution with
transition metals, Conc. HCl is used because addition of Dil. HCl adds
H2O which can cause ligand exchange.
- Cr3+ is a green solution; Cr(OH)3 is a grey-green ppt. CrO4 2- is a yellow
solution. MnO4 2- is a green solution. MnO2 is a brown solid. MnO4 2- is a purple
solution.
Na2CO3 in (aq) acts as a base and can provide OH- ions for acid-base
reaction.
Reaction Kinetics:
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The units of Rate in the rate equation is always mol dm^-3 s^-1
When using multiple-step reaction to determine the rate equation, things
to note of:
1) The equation is proportional to the reactants in the slow step.
2) If any of the reactants is present as a product in the previous fast step
(reversible), then the reaction is proportional to the reactants of the
fast step and inversely proportional to the products of the fast
reversible step.
Catalysts increase the value of rate constant by decreasing activation
energy and providing an alternative reaction pathway.
Electrolysis:
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When both the half cells of an electrochemical cell are given ( x/y ) and
(p/q), use the data booklet to determine which is the anode and cathode
first by looking at E values. Once determine already, then you can see the
observations caused by making changes to the setup.
Temperature does affect Ecell because we do not know enthalpy change
of half-cell so can be endo/exo; and POE may shift accordingly.
When they give you the electrolysis cell setup and give u the battery
terminals, remember that electron flow is opposite to conventional
current flow. That is how you will determine the anode and
cathode.
If the question asks why is the electrode ( NOT MEMBRANE )
porous ? It is to increase total surface area of electrodes to allow
reactions at electrode to occur more rapidly. The membrane is porous to
allow selective ions to pass through to maintain electrical neutrality.
When question asks why a final product is produced at an
electrode, you CANNOT use the electrolyte as a reactant. It is
usually the PRODUCTS of the electrolysis that react together to
give the final product.
Usually, the concentration of H+ is kept constant, because in
many cases, it is part of the half equations of redox reaction in
the electrolysis.
When dilute NaOH is added to an half cell, it can act as a source of OHions and react with cations to form hydroxides.
In electrolysis of sodium halide, a higher concentration of halide ion will
lower its reduction potential and in most cases, make it more likely to be
oxidized, unless its fluorine.