Вы находитесь на странице: 1из 10

Inorganic Chemistry

Group 2
1 Trends N RXNs
Oxidation Numbers

They have a ns2 configuration which allows +1 and +2 oxidation state


+3 state is not possible as removal from INNER quantum shell of
electrons
Still adopt +2 state due to lattice energy more exothermic since higher
charge and therefore more stable

Atomic Radius

Increases down the group due to increasing number of quantum shells


of electrons

Ionisation Energy

Decreases down the group as more quantum shells, stronger shielding


effect, weaker effective nuclear charge, electrostatic forces of
attraction between nucleus and outermost electron weaker, less
energy needed to remove electron

Melting/Boiling Points

Decreases down the group


Size of CATIONS increases down the group, metallic bonds between sea
of delocalized electrons and cations weaker, less energy
(for ionic compounds) Lattice energy decreases down the group as
cationic radius increases
Less energy needed to break lattice
Group 2 contributes more valence electrons per metal atom
Group 2 has a smaller cationic size due to more protons
Group 2 cations have higher charge density
(for Ionic compounds) Group 2 lattice energy therefore greater/stronger
metallic bonds

Solubility

Solubility of hydroxides increases down the group, sulfates decreases

Reactivity/Reducing Power

Group 2 metals are all reducing agents as they are oxidized


themselves to form cations

Inorganic Chemistry

Reducing strength increases down the group as effective nuclear


charge decreases down the group, easier to lose electrons (greater
ease of oxidation)
Rreactivity increases down the group

Reaction with Oxygen, Water (Redox)


[LO] Describe outcomes of RXNs of elements with oxygen and water

M + O2 = MO (Oxide)
Very slow, Slow, Fast, Explosive
Magnesium burns with brilliant white flame, Calcium burns with brick-red
flame, strontium burns with crimson-red flame, barium burns with green
flame
M + H2O = M(OH)2 + H2
Magnesium reacts with steam to give oxide and cold water to give hydroxide
Very slow with cold, slow with cold, vigorous with cold, very vigorous with
cold
Remember solubility of hydroxides increases down the group, so more
alkaline as well.

[LO] Behaviour of oxides with water


Reaction of MO with H2O

MO + H2O = M(OH)2
Lattice energy decreases down the group due to cation radius, reaction with
water increases
Reacts very slowly with cold water, rapidly with heat given off, vigorously
with heat given off, very vigorous reaction with a lot of heat given off
Talk about solubility as well

[LO] Qualitative analysis of thermal stability of NITRATES in terms of


charge density and polarisability
Thermal Stability

M(NO3)2 = MO +NO2 +1/2 O2


M(CO3) = MO + CO2 + O2
M(OH)2 = MO + H2O
Increases down the group
Cationic radius increases down the group, charge density increases down the
group since charge remains the same. Polarising power decreases down the
group, less able to distort anions electron cloud (to smaller extent). Unable to
weaken covalent bonds as much, less likely to be broken, ease of
decomposition decreases, higher decomposition temperature due to greater
thermal stability.
Polarisability of anion depends on large size of anion with large electron
cloud.

Inorganic Chemistry

Only polyatomic anions can be decomposed


Group 1 nitrates decompose to give MNO2 + 1/2O2, only lithium hydroxides
and carbonates decompose
Group 1 metals have +1 charge and larger radii, lower charge density, unable
to polarize as much, ease of decomposition decreases, greater thermal
stability, so dont decompose as much

Group 7
2 Trends N RXNs
Oxidation Numbers

They have a ns2np5 configuration which allows up to +7 O.S


Can expand octet due to presence of low lying empty d orbitals (can be
3d, 4d, 5d)
Exception is Fluorine which ends at 2p5 shell, no low lyind d subshell,
so only O.S it can possess is 0 or -1

Covalent and ionic Radii

Increase down the group due to increasing number of quantum shells..


Anion has larger radii than atom due to more number of electrons
leading to more inter-electronic repulsion, weaker effective nuclear
charge and less electrostatic forces of attraction

Bond Energy

Atomic Radius increases down the group, overlap between orbitals of


the atoms not as effective
Bond length longer, bond strength weaker
Fluorine is an exception as it has a small atomic size, therefore lone
pairs of electrons repulse each other, weakening F-F bond, easier to
break

First IE

Less endothermic down the group as atomic radius increases, effective


nuclear charge decreases less energy needed to remove electron
from outermost shell

Electron affinity

Inorganic Chemistry

Less exothermic down the group as atomic radius increases, effective


nuclear charge decreases less energy given out when electron added
to outermost shell due to less attraction

Electronegativity

Ability to attract shared pair of electrons in covalent bond towards


itself
Decreases down the group due to decreases effective nuclear charge

[LO] Trends in Volatility and analyse in terms of D.F


Volatility N MP/BP

Increasing number of electrons going down the group, larger electron


cloud, more polarizable, stronger D.F, more energy needed to
overcome D.F
MT/BL points increase down group as well

Physical States (Remember room temperature states to explain observations!) [LO]


Colour

Fluorine exists as a pale yellow gas, very pale yellow in non-polar


solvent
Chlorine exists as a yellow-green gas, colourless in dilute, pale
yellow in concentrated, pale green in nonpolar
Bromine exists as a reddish brown liquid, reddish brown when
gas, yellow when dilute, orange when concentrated, orange to RB in
non-polar solvent
Iodine exists as a shiny black solid, has dark purple gas, brown
when with iodide ions, pale yellow in water, and violet in non-polar
solvents

Relative Oxidising Power [LO] Deduce from E values relative


reactivity/oxidizing power

Halogens are oxidizing agents as they are reduced themselves


Decreases down the group as effective nuclear charge decreases down
the group, less able to attract new electrons (affinity)
E value less positive

Redox reaction with water

F2 + H2O = HF + O2
F2 + H2O = HF + O3
Fluorine reacts EXPLOSIVELY with cold water to give HF and
oxygen/ozone
CL2 + H2O = HCL + HOCL (disproportionation)
Br2 + H2O = HBR + HOBR (To a smaller extent)

Inorganic Chemistry
Displacement (Redox)

More reactive halogen can displace less reactive one from its salt

More redox with Fe, Fe2+ and Thiosulfate

Iron burns in halogen vapour to give iron trihalides


Iodine vapour can only produce iron 2 halides
Reaction less vigorous down group
Oxidise Fe2+ to Fe3+, becoming X- itself
Only chlorine and bromine and fluorine can oxidise Iron, iodine is too
weak
Chlorine and bromine can also oxidise S2O32- to give SO42Iodine can only oxidise S2O32- TO GIVE S4O62-

More redox with phosphorus, non metals

All halogens reacts with white phosphorus (P4) to give PX3


PX3 can further react in a reversible reaction to give PX5
Fluorine can react with all non-metals except noble gases, nitrogen
while chlorine and bromine will not react with nitrogen, carbon,
oxygen, NG.

More redox with Hydrogen gas [LO] Reaction with Hydrogen

Hydrogen gas react with all halogens to produce hydrogen halides


Forming H-X bond, breaking X-X bond
Bond forming is exothermic, since decrease in bond energy down
group, less exothermic down group, reaction less vigorous
Very rapid, explosive with F, rapid explosive, slow, reacts reversibly
and slowly
Remember that fluorine has anomaly of having very weak F-F bond
strength..

More disproportionation redox with alkalis and metals [LO] RXN of CHLORINES
with cold and hot aq NAOH

Cl2 + OH- = CL- + CLO- + H2O (Cold)


Cl2 + OH- = CL- + CLO3- + H2O (Hot)
Same for Bromine but with a lower temperature
Iodine will just react to form iodate ion, no IO- produced
Reacts with metal to give WHITE METALLIC SOLID SALT

MP/BP of Hydrogen Halides

HF significantly higher due to formation of intermolecular hydrogen


bonds
Increases from HCL to HBR to HI due to increasing number of electrons,
electron cloud, polarizability and DF
All are colourless gases and form white fumes in moist air

Inorganic Chemistry
Decomposition of Hydrogen Halides [LO] Thermal stability of hydrides and
interpret in terms of bond energies

HBR and HI can decomposed to give back hydrogen and halides


Involves breaking of H-X bond
Since bond strength decreases down the group, breaking of H-X bond
less endothermic down group, more easy to break the bond, thermal
stability decreases down group
HF does not decompose, HCL does not decompose, HBr decompose to
give reddish brown fumes on strong heating and HI decompose to give
purple fumes of I2 with red hot rod

Acid Strength

Depends on ability to donate proton (breaking of H-X bond)


Since bond strength decreases down group, easier to break bond to
donate proton
Therefore acid strength increases down the group
H-F is however a weak acid due to high strength of H-F bond

Precipitation reaction with Silver Nitrate and Ammonia [LO] RXN of halides with
ammonia, Ag

CL- ions react with AGNO3 to give white ppt, Br- cream, I- yellow ppt
Ag+ + NH3 = [Ag(NH3)2]+ (Position of equilibrium shifts)
Key concept is dissolving requires ionic product to be lower
than Ksp

Reaction with PB2+ ions

React with PB2+ ions to give PBX(s) which is only a yellow ppt with I
and white with rest
May be soluble upon addition of excess halides due to formation of
PB2+ + X- = [PBX4]2- complex ion

Reactions with concentrated sulfuric acid [LO] RXN with conc. Sulfuric acids

Acid base reaction


NaX + H2SO4 = NaHSO4 + HX
White misty fumes
HX is oxidized (ease of oxidation increases down the group)
NaF + H2SO4 = HF + NAHSO4 (SAME FOR CL, BR, I)
HBr + H2SO4 = BR2 + SO2 + H2O
HI + H2SO4 = I2 + S + H2O
HI + H2SO4 = I2 + H2S + H2O
To liberate CL2 / F2 from halide, use conc sulfuric acid to
oxidise to HCL/HF and NAHSO4 and further oxidise HCL/HF
with MnO2 to CL2/F2 + MnCL2 + H2O

Inorganic Chemistry

To prevent further oxidation of HBr and HI, use H3PO4 instead


to just liberate HBR, HI and NaH2PO4

Periodicity
3 Trends N RXNs
Reaction of period 3 with oxygen gas [LO] Describe rxn of elements with
oxygen

Oxygen is a strong oxidizing agent


Sodium tarnishes rapidly in air to give a white ionic solid, burns with
brilliant yellow flame
Magnesium tarnishes less rapidly in air to give white ionic solid, burns
with brilliant white flame
Aluminium oxidises easily in air to form layer of aluminium oxide that
protects it from further oxidation
Silicon oxidises in air at high temperature to form silicon dioxide
(Giant)
Phosphorus catches fire readily in air to burn with bright white flame
and produce white solid. Red phosphorus burns with bright orange
flame (P4O6)

Inorganic Chemistry

Sulfur burns on gentle heating with pale blue flame to form SO2. SO2
can be further oxidized to give SO3.
Chlorine does not react.

Reaction of period 3 with chlorine gas [LO] Describe rxns of elements with
chlorine

Sodium and magnesium burn readily in chlorine gas to give white ionic
solid. Highly exothermic.
Aluminium only reacts when dry chlorine gas is passed over heated
aluminium foil. RXN is slow at room temperature. Pale yellow ALCL3
powder produced that fumes. Form AL2CL6 dimers as well.
If chlorine passed over HEATED silicon powder, can form silicon
tetrachloride.
Burns vigorously with chlorine gas to produce PCL3 and PCL5. Excess is
used to favour PCL5 (pale yellow solid)
Rest not in syllabus

Reaction with water

Sodium reacts explosively and violently and exothermically with cold


water to produce sodium hydroxide and hydrogen
Magnesium reacts slightly with cold water and rapidly with steam
Aluminium does not react with water due to aluminium oxide
Silicon reacts with water under red-hot temperatures and steam to give
silicon dioxide
Phosphorus and sulfur do not react.
Chlorine disproportionates.

General Trends

We observe that Sodium usually always reacts, mostly without heating


Magnesium usually also reacts but with harsher conditions/slower
Aluminium only reacts with oxygen and chlorine under harsh conditions
but not with h2o
Silicon reacts with all 3 under harsh conditions
Phosphorus is very reactive, but does not react with water
Sulfur reacts with first 2 under harsh conditions, but not with water
Chlorine only reacts with water

Properties of period 3 oxides [LO] Suggest chemical bonding present in


chlorides and oxides

Change from ionic to covalency


o Due to decrease in electronegativity difference between element
and oxygen therefore more equal electron sharing since no atom
nucleus pulls electrons more towards itself
o Ionisation energy of metals low, high tendency to donate
electrons to oxygen

Inorganic Chemistry
Ionisation energy of non-metals high, high tendency to form
covalent bonds with oxygen
Melting Points
o Melting points of NaO and MgO high due to giant ionic lattice
with strong electrostatic forces of attraction between oppositely
charged ions
o Melting point of MgO higher due to stronger lattice energy due
to higher charge density, more energy needed to break apart
lattice
o Melting point of Al2O3 lower due to high charge density of
Aluminium cation, leading to polarization of anions electron
cloud, covalent character, weaker lattice energy
o SiO2 is a giant covalent structure, strong covalent bonds holding
atoms together. Each SI bonded to 4 O and each O bonded to 2
Si.
o Melting point of SO2 and P4O6 lower due to simple covalent
structure and weak VDW/D.F
Acidity. Fundamental concept of acidity deals with O2- ion hydrolyzing
in water to produce hydroxide ions
Ionic oxides are always basic [LO] Describe reaction of oxides with
water and acid base behavior of oxides and hydroxides
o NaO will dissolve fully and exothermically and vigorously in
water to give Na+ and OH- ions
o Strongly alkaline at PH13
o Also reacts with acids to produce Na+ and H2O
o MgO reacts slower and limited solubility with water due to higher
LE to give magnesium hydroxide/oxide in steam. PH is lower at 9
due to limited solubility
o MgO also reacts with acids to give Mg2+ and H2O
o Sodium Hydroxide, magnesium hydroxide react with acids to
give salt and water in neutralisation reaction
Amphoteric Oxides
o Al2O3 is insoluble in water (so does not react as previously
mentioned)
o Reacts with acids to form Al3+ ad H2O
o Reacts with STRONG excess bases and H2O to give [Al(OH)4]o Aluminium Hydroxide also reacts with acids to give Al3+ and
H2O
o Dissolves in excess strong bases to similarly form same ion. (No
water in equation)
Acidic Oxides
o Sio2 does not react with water
o Reacts with hot and concentrated strong bases before SiO32and h2o formed
o P4O6 reacts with cold water spontaneously to give acidic
solution of H3PO3
o

Inorganic Chemistry
o
o
o
o
o
o
o

P4O10 reacts with water violently to give acidic solution of


H3PO4
P4O6 dissolves in strong bases to form HPO32- and water
P4O10 dissolves in strong bases to form PO43- and water
SO2 reacts with water to give H2SO3
SO3 reacts with water to give H2SO4 in a very violent and
exothermic reaction
SO2 reacts with bases to form SO32SO3 reacts with bases to form SO42-

Physical Properties of Period 3 Chlorides

Follows the same trend as oxides just THAT


AlCL3 is a pale yellow powder and form AL2CL6 in an equilibrium
reaction where more ALCL3 formed when temp is high
SiCL4 is a colourless fuming liquid
PCL3 is a colourless fuming liquid
PCL5 is a pale yellow powder

Reactions of chloride with water (Think about salt hydrolysis) [LO] RXN of
chlorides with water

NaCl hydrolyses in water to give Na+ and Cl- ions


Since Na+ has higher charge density and Cl- is a weak base from a
strong acid, both will not hydrolyse
Neutral at PH7
MgCl2 + H2O = [Mg (H2o)6]2+ + cl[Mg(H2o)6]2+ + H2O = [Mg(H2O)5(OH)]+ + H3O+
Mg 2+ has high charge density able to undergo hydrolysis to produce
acidic 6.5 solution
AlCl3 will react with water to form Al(OH)3 and HX
In excess of water, Al3+ will hydrolyse as well to form [Al(H2O)6]3+
which will further react to form [AL(H2O5)OH]]2+ AND give acidic
solution of PH3
Adding more hydroxide ions can further deprotonate to
[Al(H2O)4(OH)2]+ AND H2O
OR TO [AL(H2O3)9(OH)3] solid and H2O
OR TO AL(H2O)4- and H2O
[Al(H2O)6]3+ can also react with carbonates to produce
[AL(H2O)3(OH)3] and H2O and CO2 (PPT is white)
Sicl4, PCL3, PCL5 will react with water violently to produce fumes of
HCL gas, forming strongly acidic solutions of PH1
Complete hydrolysis occurs where they react with water to give
SiO2.2H2O, H3PO3, H3po4 AND HCL GASS
Upon dropwise addition of water, PCL5 produces POCL3 instead and
HCL

Похожие интересы