Group Study II and VII

Group II
Alkali-earth metals Oxidation state: +2
Removal (or sharing) or two valence shell electrons ns2 Therefore, 1st and 2nd IE usually low. 3rd IE usually jumps by about 6000kJ from 2nd due to removal of electron from an INNER quantum shell

Group II trends
Radii
Atomic and ionic
INCREASES down group
increasing number of quantum shells Increasing shielding Overall decrease in Effective Nuclear Charge despite increase in proton number due to increasing shielding

Ionic radii < atomic radii

1 less quantum shell

IE
DECREASES down group
MORE quantum shells, valence electrons further, less strongly bound 2nd IE > 1st IE, because outgoing 2nd electron attracted back by single positive charge on ion after 1st electron left M+ M2+ + e-

Melting points
DECREASES down group Related to atomic radii and IE Lowered effective nuclear charge lower attraction for valence electrons metallic bonds easier to break

Group II trends
Electronegativity
DECREASES down group
Relate to atomic radii and IE EN is like measure of attraction of electrons to itself Therefore, more shell big radius lower eff. Nuc. Charge lower EN

Conductivity
INCREASES down group
Relate to atomic radii and IE also Down group IE lower electrons escape easily
So can move around and conduct electricity more easily!

Standard Reduction Potential

DECREASES down group (become more negative)
Relate to IE Down group IE lower electrons escape easily dont want them back (dont want get reduced) Eo more negative less easily reduced, more easily oxidised Meaning, down the group, reactivity INCREASES!

Beryllium
Some compounds are covalent e.g. BeCl2 Some have partially covalent character e.g. BeO Why?
Small size, high charge high charge density high polarising power distort electron cloud of anion forms a covalent bond Diagonal relationship with Al
Note similarities between AlCl3 and BeCl2 Revise how to draw the AlCl3 dimer and BeCl2 polymer! Be and Al are frequently said to be electron deficient in their covalent compounds. Dimer and polymerisation involves DATIVE BONDING

Beryllium
BeCl2 is much more volatile than MgCl2
Covalent molecule that is polymerised (not ionic) Melting and boiling involves breaking of id-id interactions

BeO and BeOH are amphoteric

BeO + H+ Be2+ + H2O BeO + 2OH- + H2O Be(OH)42 Doesnt this look like reaction of Al3+ in NaOH?

Group II Rxn with H2O

Reacts readily to give H2 gas
Reactivity INCREASES down group Products metal oxides; CaO onwards will dissolve immediately to form hydroxides
Be Rxn cond. Does not react Mg Slowly with water, fast with steam Ca Readily with water Sr Very readily Ba Most reactive

Product

none

MgO Ca(OH)2 Slightly soluble

Sr(OH)2

Ba(OH)2

Solubility increases Basicity increases

Group II Rxn with O2

Burns brilliantly when heated to give basic oxides
Reactivity INCREASES down group
Sr and Ba almost spontaneously burns in air

Be gives amphoteric oxide (due to partially covalent nature)

Be Product Behavior in water BeO None Insoluble due to partially covalent nature Mg MgO Slightly soluble to form Mg(OH)2 Ca CaO Sr SrO Ba BaO

Dissolves exothermically in water Gives hydroxides Solubility increases Basicity increases

Group II Thermal stability

Nitrates, carbonates and hydroxides decompose on heating
M(NO3)2 MO + 2NO2 + O2 MCO3 MO + CO2 M(OH)2 MO + H2O

Thermal stability INCREASES down group

Fatter radii lower charge density less polarisability polyatomic anion more stable

Group VII
Halogens Oxidation state: -1 (usually), Cl onwards can go as high as +7 F is the most electronegative, will only be -1 because no one can steal its electrons. F also cannot be more than -1 because it cannot expand octet Cl, Br, I can expand octet, share up to 7 of the valence electrons.

Group VII trends

Atomic and Ionic radii
INCREASES down the group

IE
DECREASES down the group But still relatively high, therefore they do not like to form cations, but positive oxidation states in COVALENT compounds possible (esp if bonded to O)

EN
DECREASES down the group But most electronegative in respective periods

Mp, bp
INCREASES down the group Volatility decreases as a result Larger size greater VDW interactions (id-id)

Group VII trends

Colour
INCREASES down the group
F2 pale yellow gas Cl2 pale green gas Br2 red-brown liquid, red vapor I2 black crystals, violet vapor

Solubility
Good in organic solvents Poor in water (fluorine oxidises water to O2) Iodine solubility enhanced by I3- formation

Group VII oxidising ability

Readily oxidises, and gets reduced to -1 state Oxidising ability DECREASES down group
(by now, you should realise that many trends are quite opposite to group 2)

Oxidising ability high Eo very positive

Highest for F2 (+2.87V) Lowest for I2 (+0.54V) Why?
High EN of F, high tendency to accept electrons to form octet

Group VII oxidising ability

Cl2 and Br2 oxidise S2O32- to SO42 4X2 + S2O32- + 5H2O 8X- + 2SO42- + 10H+ S changes from +2 to +6

I2 oxidises S2O32- to S4O62- only

I2 + S2O32- 2I- + S4O62-

Group VII displacements

The more reactive Halogen will displace the less reactive one.
F2 will displace Cl-, Br-, I- to form F- and Cl2, Br2, I2 Likewise, Cl2 will displace Br- and I Br2 will displace I-

Group VII Rxn with H2

H2 + X2 2HX As usual, fluorine is most reactive (wants to oxidise H to H+ very very much) Very high reactivity of fluorine can be explained by weak F-F bond energy due to lone pair repulsion on the two F.
F2 Rxn Explosive in the dark Cl2 Explosive in sunlight, slow in dark HCl Br2 Requires heat and Pt catalyst I2 Slow, equilibrium mixture HI

Product

HF

HBr

Group VII Rxn with H2

Stability of hydrogen halides
HF > HCl > HBr > HI H-F bond length shortest due to small H and F atomic radii bond strength highest Evidence
HI dissociates 33% into H2 and I2 at 1000*C HI dissociates to form the strongest acid out, followed by HBr, HCl and HF (weak acid)

Acidity
HI > HBr > HCl >>> HF HI dissociates the most completely in water

Group VII Rxn with H2

Reducing property
Ease of oxidation : HI > HBr > HCl >>>>>> HF Easy to oxidise HI and HBr back to I2 and Br2 by conc. H2SO4 HCl oxidised only by very strong oxidising agents such as KMnO4 or MnO2 Almost impossible to chemically oxidise HF

Group VII Rxn with silver

Halide test
Add AgNO3(aq) and then dilute NH3 and then conc NH3
Reagent FClBrI-

AgNO3

No ppt

White ppt AgCl Soluble soluble 1.8 x 10-10

Cream ppt AgBr Insoluble soluble 7.7 x 10-13

Yellow ppt AgI Insoluble insoluble 8.3 x 10-17

Dil NH3 Conc NH3

n/a

Ksp

Group VII Rxn with silver

NH3 addition is to form the diamminesilver complex ion [Ag(NH3)2]+ This decreases ionic product [Ag+][X-] For AgI, Ksp is so low that even the decrease of ionic product by NH3 is still higher than Ksp of AgI stay insoluble

Group VII Rxn with conc H2SO4

H2SO4 serves to force halide ions to accept back a H+ and form HX which escapes as white fumes It can also be an oxidising agent in the case of HBr and HI to give Br2 and I2

Group VII Rxn with conc H2SO4

Reaction with H2SO4 Reaction with MnO2 Cannot be oxidised Observation FNo oxidation at all White HF fumes

Cl-

Cannot be oxidised with H2SO4 but possible with MnO2 added

2HBr + H2SO4 Br2 + SO2 + 2H2O

4HCl + MnO2 Cl2 + MnCl2 + 2H2O

Cl2 gas evolved with white HCl fumes

Br2 gas evolved with some white HBr fumes I2 gas evolved, very little HI fumes

Br-

I-

8HI + H2SO4 4I2 + H2S + 4H2O

Group VII - Misc

Chlorine with aq NaOH
Cold dilute NaOH
Disproportionation (1 ox state become 2 different ox state) Cl2 + 2OH- Cl- + ClO- + H2O

Warming to 70*C, ClO- disproportionates further

3ClO- 2Cl- + ClO3-

Chlorine with hot aq NaOH

3Cl2 + 6OH- 5Cl- + ClO3- + 3H2O