------------------ 12. KOLTHOFF, T. M. & WILLMAN, A., J. Am. chem. Soc.,56 (1934), 1007.

13. Fuoss, R. M. & KRAUS, c. A., J. Am. chem. Soc., 55(1933), 2387. .'

14. HARRIS, M. C. & MILNE, J. B., Can. J. Chem., 50 (1972),3789. ,

Taken (g) Found (g) Taken (g) Found (g) 15. MALHOTRA, K. C. & SUD, R. G., J. inorg. nucl. Chem.,38 (1976), 775.

16: PAUL, R. c., VASHISHT, S. K., MALHOTRA, K. C. & PAHIL,S. S., Analyt, Chem., 34 (1962), 820.

. 17. PAUL, R. C., PAHIL, S. S., MALHOTRA, K. C. & VASHISHT,•.•. S. K., J. scient. indo Res., 41 (1962), 2113.

18. PAUL, R. c., SINGH, D. & MALHOTRA, K. c., Z. anorg.Chem.,321 (1963), 61-

19. HALL, N. F., "I. Am. chem. so«, 52 (1930), 5115.

r

TABLE 1- ESTIMATION OF BASES IN FUSED PHENOL USINGHS03F AS TITRANT

BasePotentiomet~ically . Conductometrically

(0.05N HSOaF) (0.25N HSOaF)

Pyridine 0.1775 0.1772 0.3350 0.3550rticoline 0.2375 0.2371 0.4750 0.4743

orpholine 0.2125 0.2123 0.4250 0.4250Urea 0.1500 0.1501 0.3000 0.2988Benzamide 0.3025 0.3019 0.6050 0.6039Thiourea 0.2750 0.2743 0.5500 0.5492Piperidine 0.2125 0.2125 0.4250 0.4242Acetamide 0.1025 0.1021 0.2050 0.2055Quinoline 0.3225 0.3225 0.6450 0.6444

TABLE 2 - ESTIMATION OF MIXTURES OF BASES IN PHENOLUSING HS03F AS TITRANT

Taken (g) Found (g)Mixture

I II I II

Triethylamine(l) +Pyridine(U) 0.8372

Pyridinefl) +Thiourea(LI) 0.6540

Urea(I +Acetamide(II) 0.3213

Sodium phenoxidetl)+ Urea(II) 0.4438

0.8369

0.6537

0.3203

0.4438

0.36xO

0.3812

0.3608

0.3810

0.2721

0.2851

0.2729

0.2854

these bases. The results of these estimations aregiven in Tables 1 and 2.

These studies have been extended to the esti-mation of mixtures of bases with the help of fluoro-sulphuric acid in fused phenol (Table 2). The resultsfor binary mixtures are within the experimentalerror. However, for mixtures of three or more bases,good results could not be obtained. The potentialjump near the end point is of the order of 100 mVto 150 mV. Visual titrations with the help oftraditional indicators like malachite green andcrystal violet have also been carried out conveni-ently.

Thanks are due to the CSIR New Delhi for theaward of a junior research fellowship to one of us(V. P. M.).

References1. MALHOTRA, K. C., MAHAJAN, R. K. & CHAUDHRY, S. C,.

Indian J. Chem., 14A (1976), 1017. .2. MALHOTRA, K. c., MEHROTRA, G. & CHAUDHRY, S. c., J.

inorg . nuc!. Chem., (Communicated).3. MALHOTRA, K. C., MAHAJAN, V. P. & SUD, R. G., Aust.

J. Chem., 32 (1979), 1039. .4. KENDALL, J. & BooGE, J. E., J. chem. Soc., (1925), 1768.5 CHEsTERMAN, D. R., J. chem. Soc., (1935), 906.6: FAILKOY, Y. Y. & ZHlKHAREV, V. S., zt: obshch. Khim.,

33 (1963), 3789.7. BIRCHALL, T., BoURNS, A. N., GILLESPIE, R. J. & SMITH,

P. J., Can. J. Chem., 43 (1964), 1433.8. MALHOTRA, K. C. & BALI, A. K., Indian J. Chem., 13

(1975), 699. .9. MAYER, J. & SCHRAMM, G., Z. anorg, Chem., 24 (1932),

206. (A)10. GILLESPIE, R. J. & MALHOTRA, K. c., J. chem. Soc. ,(1967), 1994.

11. GILLESPIE, R. J., J. chem. Soc., (1950), 2537.

(

NOTES

Chlorosulphuric Acid as a Non-aqueous Solvent :Part XI-Behaviour of Some Acid Halides in ChIoro-

sulphuric Acid

RAM C. PAUL, D. S. DHILLON, D. KONWER & J. K. PURI*Department of Chemistry, Punjab University, Chandigarh 160014

Received 2 December 1978; revised 29 March 1979;accepted 24 April 1979

Behaviour of various inorganic and organic acid halides inchlorosulphuric acid reveals that selenyl, propionyl, n-butyryl,isobutyryl and benzoyl chlorides behave as strong bases. Phos-phoryl and thiophosphoryl bromides, acetyl, phenylacetyl, mono-chloroacetyl and succinyl chlorides behave as weak bases. Substi-tution of chlorine or nitro group on benzoyl chloride has verylittle effect on its basicity. Phosphoryl fluoride and chloride,sulphuryl, thionyl and oxalyl chlorides behave as non-electrolytesin chlorosulphuric acid.

FROM a study of the behaviour of acid .halidesin disulphuric acid: Paul et al-, inferred that

acid halides could be classified into two categories :(i) those having predominantly a basic oxygen and

. (ii) those having an ionizable halide ion. Butin disulphuric acid their basicities could not ·bedifferentiated because of the levelling effect. Aschlorosulphuric-acid is a weaker acid than disul-phuric acid, a 'systematic study of the behaviour ofthe acid halides in it, is considered· helpful indifferentiating their>basicities. .

Chlorosulphuric acid (BDH, reagent grade) wasused directly as suggested by Robinson andCiruna", All the conductance measurements werecarried out as reported earlierv'". ; The conducto,metric factor (y) was determined by the. methodmentioned elsewhere". )

The acid halides (commercial samples) were puri-tied by the usual methods. Phosphoryl fluoridewas prepared and purified' by the known method"Carbonyl chloride was prepared by reacting carbontetrachloride with oleum, and dried by passingthrough 98 % sulphuric acid.

Most of the solutes behave 'as bases in HSOaCI(Eq.1)

B + HSOaCI ---+ BH+ + S03CI- ... (1)But the solutes having ionizable chloride ion formhydrochloric acid (Eq. 2) )

INDIAN J. CHEM., VOL. 18A, NOVEMBER 1979

(CHa)2 C6H2COCl +HSOaCl-+(CHa)2C6H2CO++ SOaC1- + HCI ... (10)

Phenylacetyl chloride initially forms yellow sol-ution in HSOaCl, which finally changes to darkbrown due to some sulphonation reaction. How-ever, conductance data of the solutions indicate thatit behaves as a weak base in this solvent.

Monochloroacetyl chloride gives fairly conducting._solutions in HS03CI and behaves as a weak base.

POBr + 3HSO CI -+ PO (SO CI) + 3HBr . ,,(4) J:?ichloroacetyl chlor~de ~nd trichloroacetyl chlo-3 a a a nde when dissolved In this solvent behave as non-

The solvolysed product, i. e., PO (S03Cl)3 formed electrolytes. From t~es~ observations it. is con-in reaction (4) gets protonated to a very little extent ~luded that th~ substitution of electrone.gatIve .a~omand further behaves as a very weak base in HSOaCl. In acetyl chlonde has a greater effect on Its basicity,

Triphenylphosphine oxide and triethyl phosphate Solutiof:1S or propionyl, n-l;>utyryland ~sobuty-form highly conducting solutions and thus behave ryl chion des In HSOaCI are highly conducting andas strong bases . thus behave as strong bases.

. Bergmann and Radt" has reported the addition(C6H5)3PO+ HS03 CI -+ (C6H5)aPoH+ + SOa Cl- compounds of sulphuric acid and benzoyl chloride .

. ,,(5) Benzoyl chloride forms highly conducting solutionsin HS03CI and thus behaves as a strong base. Fur-ther the conductance data of the solutions of o-chlo-robenzoyl, p-chlorobenzoyl, m-nitrobenzoyl andp-nitrobenzoyl chlorides in chlorosulphuric acidsuggest that the introduction of chlorine or nitrogroup on benzoyl chloride has very little effect onits basicity. Oxalyl chloride when dissolved inchlorosulphuric acid behaves as a non-electrolytewhereas succinyl chloride behaves as a weak basein this solvent.

MCI + HS03CI---+- M+ + S03CI- + HCI ".(2)Hydrochloric acid further behaves as a very weakbase" in HSOaCl.

Phosphoryl chloride and fluoride behave as n011-electrolytes in chlorosulphuric acid, whereas phos-phoryl bromide behaves as a weak base in it :

POBr3 + HS03CI -+ P (OH+) Br3 + S03CI- .,,(3)

or

From the above observations it is concluded thatthe substitution of Cl or F in place of phenyl orethoxy group in triphenylphosphine oxide andtriethyl phosphate decreases the basicity of oxygentoa greater extent which is evident from the non-electrolytic behaviour of phosphoryl chloride andfluoride in HSOaCl. Thiophosphoryl bromidebehaves as a weak base (Eq. 7) :

PSBr + HS03CI -+ P(SH+)Br3 + S03CI- ".(7)Selenyl chloride behaves as a fully protonated base(Eq. 8).

SeOCl2 + HSOaCI -+Se (OH+) Cl2 + S03CI- .,,(8)

Thionyl chloride and sulphuryl chloride also behaveas non-electrolytes in HS03Cl.

Acetyl chloride is reported to form acetylsul-phuric acid'>. Raman spectral a of the solutionsof acetyl chloride in H2S04 provide condusiveevidence for the protonation of acetyl chloride. In-complete protonation of acetyl chloride has beenreported by Liler--. But in disulphuric acid, acetylchloride has been shown to form acyl ion (R-C =0+), instead of protonation. Raman - spectra"of acetyl chloride solutions in chlorosulphuric acid,also, support the formation of acyl ions. In thepresent investigations acetyl chloride gives highlyconducting solutions (Fig. 1) in HS03 CI due topartial ionization (Eq. 9)

CH3COCI+ HS03CI-+ CHaCO+ + SOaCI- + HCI.' . (9)

\ J-..

IR spectrum of the above solution shows an intenseband at 2300 crrr-' which is attributed to the for-mation -of acyl ions in this solvent.

Unlike the behaviour of acetyl chloride in chloro-sulphuric acid, -mesitoyt chloride has been shownto be fully, -ionized to. give the .mesitoyl cation"(Eq. 10)

444

,(

References1. PAUL, R. C., KAPILA,V. P. & MALHOTRA,K. c., J. chem.

Soc. (1970), 2267.2. ROBINSON,E. A. & CrRUNA, J. A., Can. J. Chem., 46

(1968), 1719.3. PAUL, R. c., PURl, J. K. & MALHOTRA,K. c., J. inorg.

nucl. Chem., 33 (1971), 2459.4. PAUL, R. C., PURl, J. K. & MALHOTRA, K. c., J. inorg.

nue!. Chem., 33 (1971), 4191.5. PAUL, R. C., DHILLON, D. S. & PURl, J. K., Indian J.

Chem., 13 (1975), 1058.6. BRAUER, G., Handbook a/preparative inorganic chemistry

Vol. 1, (Academic Press, New York), 1963, 193.7. PAUL, R. c., VASISHT,S. K., MALHOTRA,K. C. & PAHIL,

S. S., J. scient, indo Res., 2IB (1962), 528.8. GUTMANN,V. & BAAZ, M., Mh. Chem., 90 (1959), 271.9. PAUL, R. C. & VASISHT, S. K., J Indian chem. Soc., 43

(1966), 141.10. PAUL, R. c., MALHOTRA,K. C. & SINGH, G., J. Indian

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France (1972), t617. .

16-.ROBINSON,.E. A. & ClRUNA, J. A., J. Arn. chem. Soc.,86 (1964), 5677.

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,\\