periodicity
repeating pattern/trends (of physical or chemical properties)
period 3: atomic radius
decreases along the period
increased nuclear charge for same number of electron shells and shielding, produces greater attraction to outer electron
period 3: ionisation energy
increases along the period
decreased atomic radius and increased nuclear charge, more energy required to remove electrons
period 3: melting point (Na, Mg, Al)
metallic bonding
high melting point as there is a strong electrostatic attraction between delocalised electrons and positive metal ions
Al the highest because greater positive charge on ions and more free electrons, greater electrostatic attraction
period 3: melting point (Si)
macromolecular
highest melting point because must overcome strong covalent bonds, requiring lots of energy.
period 3: melting point (P, S, Cl)
simple molecule
lower melting point as only held together by weak van der Waal intermolecular forces, requiring little energy
S > P > Cl because S8, P4, Cl2 and greater the Mr, the greater the surface area for van der Waals, more van der Waals, more energy to overcome
period 3: melting point (Ar)
simple molecule
exist as single atoms so weak van der Waals and small Mr
group 2: atomic radius
increase down the group
add new shell, increasing distance to outer electron, increased shielding, reducing nuclear attraction
group 2: ionisation energy
decreases down the group
new shells, atomic radius increases, increased shielding, reduces nuclear attraction, less energy to remove an electron
group 2: melting point
decreases down the group
metallic bonding: larger the ion within the lattice weakens the attractive force as it acts over a larger distance between positive nucleus and delocalised electrons
group 2: reacting with water
M(s) + 2H2O(l) → M(OH)2(aq) + H2(g)
increase in reactivity down the group
Mg very slow: forms layer of Mg(OH)2 which is sparingly soluble so stops the reaction
weak alkaline solution
Mg with steam
Mg(s) + H2O(g) → MgO(s) + H2(g)
Mg in extraction of titanium
TiCl4 + 2Mg → 2MgCl2 + Ti
displacement reaction
RP4: test for group 2 cations (NaOH)
initially add 10 drops NaOH
MgCl2, CaCl2, SrCl2 = slight white ppt
BaCl2 = colourless solution
add excess NaOH
MgCl2 = white ppt
CaCl2, SrCl2 = slight white ppt
BaCl2 = colourless
because Mg(OH)2 is sparingly soluble
RP4: test for group 2 cations (H2SO4)
initially add 10 drops H2SO4
BaCl2, SrCl2 = white ppt
MgCl2, CaCl2 = slight white ppt
add excess H2SO4
BaCl2, SrCl2 = white ppt
CaCl2 = slight white ppt
MgCl2 = colourless solution
group 2: solubility of hydroxides
increases in solubility down the group
Mg(OH)2 is sparingly soluble
use of Mg(OH)2
milk of magnesia is used as an antacid as it neutralises stomach acid, for indigestion
use of Ca(OH)2
slaked lime is used in agriculture to raise the pH of a field (is basic)
use of CaO/CaCO3
to remove SO2 from flue gases, prevent the release into atmosphere
CaO + 2H2O + SO2 → CaSO3 + 2H2O
CaCO3 + 2SO2 + H2O → Ca(HSO3)2 + CO2
group 2: solubility of sulfates
decrease in solubility down the group
BaSO4 is insoluble
use of BaSO4
barium meal is digested and pass through digestive system, allowing the outlining of the gut by medical x-rays
it is completely insoluble so will not dissolve into blood, despite being toxic
RP4: test for sulfate ions
acidify solution with HNO3/HCl
(to remove CO2, which if present forms a false positive)
add BaCl2
white precipitate if present (as BaSO4 is formed)
RP4: test for carbonate ions
add HCl
collect gas formed
bubble through limewater (Ca(OH)2)
cloudy, white solution if present
RP4: test for ammonium ions
add equal amount of NaOH
heat the sample
place moist, red litmus over the mouth of tube as gas give off is ammonia
will turn blue
NH4+ + OH- → NH3 + H2O
RP4: test for hydroxide ions
turns red litmus paper blue
either by dipping it in NaOH solution
or
place moist, red litmus paper in petri dish with ammonia solution (on filter paper) on the other side, ammonia vapour will turn paper blue
group 7: boiling point
increases down the group
atomic radius increases increasing the strength of the van der Waal forces, greater Mr has greater surface for them to act on
I = solid, Br = liquid, Cl = gas
group 7: reducing agent
must be oxidised itself, lose its own electron
halide ions (I-) are best, most likely to lose electrons
increase down the group
atomic radius and shielding increases, reduces nuclear attraction
group 7: oxidising agent
must be reduced itself, gain electrons
halogen (F2) molecules are best, most likely to gain electrons
decrease down the group
atomic radius and shielding increases, reduces nuclear attraction less attraction to electrons
group 7: electronegativity
decrease down the group
atomic radius and shielding increases, reduces nuclear attraction less attraction to electrons
group 7: displacement reactions
Cl displaces Br = orange/red colour
Cl/Br displaces I = black precipitate
RP4: test for halide ion
add HNO3
prevents false positive from carbonate ions
add AgNO3
Ag+(aq) + X- → AgX(s)
AgCl = white precipitate
AgBr = cream precipitate
AgI = yellow precipitate
RP4: test for silver halide ions solubility
add dilute ammonia
AgCl will dissolve, precipitate disappears
AgCl + NH3 → [Ag(NH3)2]+ + Cl-
add concentrated ammonia
AgBr will dissolve
AgI is insoluble
sodium chloride + sulfuric acid
H2SO4(l) + NaCl(s) → HCl(g) + NaHSO4(s)
HCl = white misty fumes
sodium bromide + sulfuric acid
H2SO4(l) + NaBr(s) → HBr(g) + NaHSO4(s)
2HBr(g) + H2SO4(l) → Br2(g) + SO2(g) + 2H2O(l)
HBr = white misty fumes
Br2 = reddish-brown gas
SO2 = choking fumes?
Br- acting as reducing agent
sodium iodide + sulfuric acid
H2SO4(l) + NaI(s) → HI(g) + NaHSO4(s)
2HI(g) + H2SO4(l) → I2(s) + SO2(g) + 2H2O(l)
6HI(g) + H2SO4(l) → 3I2(s) + S(s) + 4H2O(l)
8HI(g) + H2SO4(l) → 4I2(s) + H2S(g) + 4H2O(l)
HI = white misty fumes
I2 = violet/purple vapour
SO2 = choking fumes?
S = yellow solid
H2S = toxic, bad smelling gas
chlorine with cold, dilute NaOH(aq)
Cl2(aq) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)
NaClO =household bleach that can kill bacteria, water treatment, and bleach paper and textiles
chlorine and water (no sunlight)
Cl2 + H2O → ClO- + Cl- + 2H+
Cl2 + H2O → HClO + HCl
disproportionation reaction
chlorine and water (sunlight)
2Cl2 + 2H2O → 4HCl + O2
UV light is present
chlorine: water treatment
(+) kills disease-causing microorganisms
prevents algae growth
(-) chlorine is harmful, respiratory and carcinogenic
organic chlorine compounds harmful to environment
(=) however, benefits outweigh the negatives
sodium with water
reacts vigorously with cold water, fizzing H2 gas and forms a ball
producing strong alkaline solution
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
sodium is more reactive than magnesium as it requires less energy to remove 1 electron than 2, more energy need to form Mg2+ ions
period 3: oxides
Na2O, MgO, Al2O3, SiO2, P4O10, SO2 and SO3
sodium with oxygen
magnesium with oxygen
aluminium with oxygen
2Na + 1/2O2 → Na2O(s)
Mg + 1/2O2 → MgO(s)
2Al + 1 1/2O2 → Al2O3(s)
silicon with oxygen
phosphorus and oxygen
sulfur and oxygen
Si + O2 → SiO2(s)
P4 + 5O2 → P4O10(s)
S + O2 → SO2(g)
sodium, magnesium, and aluminium oxide structure and bonding
giant ionic lattice
strong attractive forces between ions
MgO > Na2O (mp) Mg2+ attract the O2- more greatly
MgO > Al2O3 (mp) Al3+ distorts electron cloud of O2- and some covalent character lowers E
silicon oxide structure and bonding
macromolecular
many strong covalent bonds to overcome, requiring lots of energy
phosphorus and sulfur oxide structure and bonding
simple molecular
weak intermolecular bonds, require little E to overcome
ionic oxides with water (not aluminium)
Na2O + H2O → 2NaOH
MgO + H2O → Mg(OH)2
alkaline solutions pH 12-14 and 9-10 respectively
simple covalent oxides with water
eg. P4O10 + 6H2O → 4H3PO4(aq)
acidic solutions, pH 0-2
silicon and aluminium oxide with water
SiO2 = insoluble
Al2O3 = amphoteric, insoluble
amphoteric
will react with acid and base to form a salt
(acting as either acid/base)
basic oxides
eg. 2HCl + MgO → MgCl2 + H2O
react with acid to form salt
MgO and Na2O
acidic oxides
eg. 12NaOH + P4O10 → 4Na3PO4 + 6H2O
react with base to form salt
SiO2, P4O10, SO2 and SO3
amphoteric oxides
acting as acid with base
2NaOH + Al2O3 + 3H2O → 2NaAl(OH)4
sodium tetrahydroxoaluminate
acting as base with acid
Al2O3 + 3H2SO4 → Al2(SO4)3 + 3H2O
transition metal
elements with incomplete d-subshell that can form at least one stable ion with an incomplete d-subshell
complex
central metal atom/ion surrounded by ligands
ligand
molecule/ion that forms a co-ordinate bond with a transition metal by donating a pair of electrons
co-ordination number
number of co-ordinate bonds to the central metal atom/ion
chelate effect
bidentate/multidentate more energetically favourable than monodentate
because entropy change is always positive as there is a net increase in the number of particles
so ΔG = negative
cis-trans isomerism
occurs in square planar and octahedral complexes
cis = 90°
trans = 180°
could cause change in properties due to polarity
optical isomerism
occurs in tetrahedral and octahedral complexes
a mirror image of the 2 complexes that are not superimposable
cis-platin
Pt bound to 2 Cl- ions and 2 NH3 molecules, ligands 90° from the same molecule, square planar structure
binds to DNA, prevents cell division, and tumour growth
Tollens’ reagent
Ag+ forms linear complex
[Ag(NH3)2]+
reduced to metallic silver to distinguish aldehydes and ketones
formation of coloured ions
colour arises when some wavelengths of visible light are absorbed and the remaining wavelengths are transmitted
d-electrons move from ground state to an excited state when light is absorbed
energy of visible light equation
E = hf = hc/λ
E = energy of visible light (J)
h = Planck’s constant (6.63 x10-34)
f = frequency of light (Hz or s-1)
c = speed of light (3 x8 ms-1)
λ = wavelength of light (m)
factors affecting change in energy, electron promotion
type of ligand
co-ordination number
oxidation state (change in)
colour: type of ligand
different ligands will split d-orbital by different energies
depends on the repulsion of each ligand
colour: co-ordination number
influences strength of metal ion-ligand interaction
colour: oxidation state
strength of metal-ion ligand interactions varies due to nuclear charge
eg. Mn(II) = Fe(III) electron configuration
however, Fe(III) has greater nuclear charge so its change in energy is greater, absorbing visible light of greater energy.
heterogenous catalyst
catalyst in a different state/phase from the reactants
reactions occur at the active site on the surface
homogenous catalyst
catalyst in the same state/phase as the reactants
reactions proceed through an intermediate species
contact process
2SO2 + O2 → 2SO3
catalyst = V2O5
2SO2 + 2V2O5 → 2V2O4 + 2SO3
O2 + 2V2O4 → 2V2O5
Haber process
N2 + 3H2 → 2NH3
catalyst = Fe
N2 and H2 diffuse to Fe surface and adsorb to it, weakening their covalent bonds so reaction can take place
product molecule desorbs from surface
I- and S2O82-
overall = S2O82- + 2I- → I2 + 2SO42-
catalyst = Fe2+ ions
S2O82- + 2Fe2+ → 2SO42- + 2Fe3+
2I- + 2Fe3+ → I2 + 2Fe2+
Fe acts as reducing and oxidising agent
both negative ions so require catalyst as they repel and activation energy is high
autocatalysis example
overall:
2MnO4- + 5C2O42- + 16H+ → 2Mn2+ + 10CO2 + 8H2O
catalyst = Mn2+
how Mn2+ acts as catalyst
4Mn2+ + MnO4- + 8H+ → 5Mn3+ + 4H2O
2Mn3+ + C2O42- → 2Mn2+ + 2CO2
Lewis acid and base
Lewis acid = accept lone pair
Lewis base = donate lone pair
metal complex = central metal ion = acid, ligand = base
acidity of M3+ and M2+
acidity of M3+ is greater than M2+
M3+ is smaller with a higher charge density than M2+, more strongly polarising
M3+ pulls the O’s electrons of H2O more greatly, weakening the O-H bond, H+ is more easily released
acidity equations
eg. [Fe(H2O)6]3+ ⇌ [Fe(H2O)5OH]2+ + H+
amphoteric character in complexes
aluminium hydroxides dissolve in acids and base
in acid = [Al(H2O)6]3+
in neutral = Al(H2O)3(OH)3
in base = [Al(OH)4]-