Pseudo halogens

Pseudo halogens

• These are dimeric molecules made up of two or more

electronegetive atoms.

• They resemble halogens in many respects. Hence called

pseudo halogens; their salts are pseudo halides.
• Examples:

• Cyanogen (CN)2;cyanide ion, CN-;

• Isocyanogen, (NC)2; isocyanide NC-,
• Thiocyanogen (SCN)2; thiocyanate, SCN- ;
• Isothiocyanogen, (NCS)2; isothiocyanate, NCS-,
• Selenocyanogen, (SeCN)2 ; slenocyanate, SeCN-,
 Comparison of halogens and pseudo halogens:

• Similarities:
• Like halogens, these are dimeric and fairly volatile.

• Isomorphous with halogens. Cl2 is isomorphous to (CN)2.

• Like halogens, these also add across C=C bond

• Reaction with alkalies:
• (SCN)2 with KOH forms pot.thiocyanate & hypothiocyanate .

• This is similar to reaction of Cl2 with KOH forming pot.chloride

& hypochlorate.
• They form monobasic hydracids like halogens.
• (CN)2 + H2 --- 2HCN
• Cl2 + H2 ---- 2HCl.

• Like halogens, pseudo halogens are also oxidizing.

• ½ Br2 + e -- Br- ; Eo = 1.07V
• ½ (SCN)2 + e --- SCN- ; Eo = 0.77V

• The oxidizing power is in the order:

• F2 > Cl2 > Br2 > (CN)2 > I2 > (SCN)2 > (SeCN)2.
• Dissimilarity:
• Pseudo halogens polymerize but halogens do not.
• n(CN) --- (CN)n
• n(SCN) --- (SCN)n
• n(SeCN) --- (SeCN)n.
Cyanogen, (CN)2.
 Cyanogen

• Preparation:
• 1. By heating silver or mercuric cyanide
• Ag(CN)2 -- Ag + (CN)2; Hg(CN)2 -- Hg + (CN)2 .

• 2. Better yield is obtained by heating Hg(CN)2 with HgCl2 .

• Hg(CN)2 + HgCl2 --- Hg2Cl2 + (CN)2 .

• 3. Also by the action of KCN on CuSO4 solution.

• KCN + CuSO4 --- 2Cu(CN)2;
• 2Cu(CN)2 --- 2Cu(CN) + (CN)2.
• Properties:
• (CN)2 is a colorless gas, highly poisonous, flammable.
• Chemical reactions;
• 1. With alkalies it forms cyanide & oxycyanide.
• (CN)2 + 2KOH --- KCN + KCNO + H2O.

• 2. Slowly hydrolyses in water giving a number of products like

oxamide, amm.oxalate, HCN, HCNO, amm.cyanate,
urea,etc.

• 2. With H2S, it forms thiocyanoformide - ditioformaide

• (CN)2 + H2S - NH2CSCN;
• NH2CSCN + H2S --- NH2CSCNH2.
• 3. On reduction with H2 forms ethylene diamine.
• (CN)2 + 4H2 ---H2N-CH2-CH2-NH2.

• 4. Polymerizes at 500oC giving paracyanogen, (CN)n.

•
• Structure and bonding:

• Reduction of (CN)2 gives ethylene diamine,

H2N-CH2-CH2-NH2. This indicates a linear structure with
N ≡ C - C ≡ N linkage.

• Both the C & N atoms undergo sp hybridization

• The two Carbons use sp hybridized orbital to form a σ C-C
bond.
• The bond between C & N is a σ + 2π bond
• The lp on N occupies the remaining sp orbital.