ALKANE SULFONATES Many possible ways of synthesis-sulfochlorination (rxn.

of alkanes with SO2+Cl2 to alkane sulfonyl chloride) & sulfoxidation (rxn. of alkanes with SO2+O2 to sulfonic acid) both followed by alkali neutralisation are of commercial importance-mixt. of linear alkanes having C12-C18 chain lengths as starting materials-both rxns. proceed via radical mechanism Chemistry of rxns. R+SO2 RSO2 RSO2Cl+Cl

RSO2+Cl2 Cl+RH

R+HCl RSO2Cl+HCl

RH+SO2+Cl2

R+SO2

RSO2 RSO2O2 R+RSO2O2H RSO2O2H i.e. sulfoperoxy acids

RSO2+O2

RSO2O2+RH RH+SO2+O2

The rxn. can be started by radical initiators (peroxides) or by UV irradiations-sulfoperoxy acids being unstable, decompose to generate addnl. radicals RSO2O2H RSO3+RH OH+RH RSO3+OH R+RSO3H R+H2O 2R+RSO3H+H2O

3RH+SO2+O2

Newly formed radicals compensate for deficit due to termination rxn.-decomposition of peroxy acids results into various by products viz.esters, alcohols,discoloring substances due oxidn. adversely affecting product qualityrxn. carried out industrially with addn. of water which together with SO2 present traps the acid before its radical generating decomposition RSO2O2H+SO2+H2O RSO3H+H2SO4

In both processes-substitution mainly at the internal secondary carbon atom-oxysulfonyl grs. distributed along the whole aliphatic chain-degree of polysulfonation with in conversion RCH2CH3+SO2+O2 RCH(SO3H)CH3 RCH(SO3Na)CH3

Alkane sulfonates below C8 are not surfactant-C12-C18 sulfonates highly water-soluble-solublity because of presence of disulfonate fraction in industrial productsbeing secondary sulfonates, good wetting propertiespreferably used in detergents, cleansing agents & washing powders-widely used in emulsion polymerisation rxnsAlkane sulfonates obtained from sulfochlorination process are known Mersolates-rxn. proceeds in 2 stepsliq. paraffin reacted at 20-40C with approx. equimolar mixt. of SO2 & Cl2 under irradiation of Hg vapor lampconversion adjusted to ~ 30%-rxn. contains ~94% mono & ~6% disulfochlorides-mixt. of degassed sulfochlorides neutralized with 10% NaOH strictly <60C-at elevated (>80C) temp. sulfochloride desulfonates to alkyl chloride with liberation of SO2-salt obtained melted solidified on cooling drums & scrapped to flakes Alkane sulfonyl chloride reacted with glycine to obtain alkane sulfonamido carboxylic acids-used as effective emulsifiers & corrosion inhibitors-their esters used as plasticizers RSO2Cl+H2NCH2COOH RSO2NHCH2COOH RSO2NHCH2COOR R=Aliphatic or Phenolic fragment

The sulfochlorination process involves formation of di- & polysubstitutions in addn. to mono-to minimise these coversion limited to ~10% & unreacted recycled-rxn. at 20-40C-mixt. to settler-degassing under mild suctiondissolved SO2 removed-further conc. achieved by distilling water at 60-120C under suction-discoloration occurs-bleaching by H2O2-rxn. mixt. neutralized with NaOH-unreacted alkane removed in thin-film evaporator at ~200C under high vac.-distillate recycled-sulfonate melt solidified on cooling drum & flaked The sepn. of H2SO4 & sulfonic acid/alkane mixt. achieved by extn. with polar solvent viz. higher alcohols, ketones, ethers, etc. These sulfonates-highly water-soluble surfactantspreferably used in liq. products or concentratesapplications in detergents, personal care products, cleansers & dish-washing formulations-these are easily biodegradable in aerobic conditions but fail under anaerobic conditions