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Separation and gravimetric determination of barium using sulfadimethoxin salicylaldimine
MlCROCHEMlCAL
J”“RNAL
22, 92-95 (1977)
Separation and Gravimetric Determination of Barium Using Sulfadimethoxin Salicylaldimine PRABUDDHA Department
JAIN
of Chemistry,
AND KAMAL Holkar
Received
K.
CHATURVEDI
Science College.
Indore,
India
April 6, 1976
INTRODUCTION
Perusal of literature reveals that condensation products of sulfadiazines with salicylaldehyde and substituted salicylaldehyde are not only good bacteriostatic agents (12, 13), but are also good complexing agents (5-8). Sulfadimethoxin salicylaldimine (SUDMSA) has the system -0-C=C-C=N, similar to many precipitating agents used for a number of transition metal ions. The reagents having such a system have been investigated by a number of workers (4). The present work deals with chelates formation of SUDMSA with Ba(I1). EXPERIMENTAL Chemicals
All chemicals employed were of Analar grade. Reagents
The aqueous stock solution of barium chloride was prepared by dissolving 1 g of BaCl, in a liter of double-distilled water. The contents of barium were determined volumetrically (15) and a stock solution of the 0.001 M concentration was prepared by appropriate dilution. SUDMSA was synthesized by the procedure described earlier (9). A 1% solution of the masking reagents was prepared by dissolving the requisite amount in double-distilled water. Procedure
Barium chloride solution (5 ml, 0.01 M) was diluted to 100 ml and warmed. To the hot solution, a solution of the reagent (a slight excess was used) was added with stirring. The pH of the resulting solution was adjusted to 6.00. The white precipitate of the complex formed settled down on digestion for 30 min on water bath leaving a clear supernatant liquid. The precipitates were filtered through a sintered glass crucible of the porosity G-4 and were washed thoroughly with hot water and finally with 20% alcohol-water solution. The barium complex thus obtained was dried at 115-120°C. and weighed as (C,,H,,O,N,S),Ba. 92 Copyright All richts
@ 1977 by Academic Press. Inc. of renrodrrction in IVY fnrm re*rrurri
93 Separation of Barium from Other Metal Ions With a view to separate barium from the other metal ions, a 14.56 ml (0.01 M) solution of barium chloride was mixed with a known amount of desired foreign metal ions (40 mg) and diluted to 100 ml. A 5-ml portion of 1% masking reagent solution was added and the contents were warmed. To the hot solution, a solution of the reagent (a slight excess was used) was added and the pH was adjusted to 6.0. The complex so formed was allowed to stand on water bath for 30 min. Thus. barium could be separated and precipitated quantitatively in the presence of Ag(I), Mn(II), Cu(II), Ni(II), Co(II), Cd(II), Zn(I1). Hg(II), Pd(II), Ca(II), Sr(I1). Cr(II1). Fe(III), Mg(II), As(III), Sb(III), Sn(IV). Tl(I), and ZrO(II)(Tables 1 & 2).
S. No
0.01 M BaCl, (ml)
I.
10.00
2. 3.
20.00 30.00
Barium taken (mg)
Weight of complex (w)
Barium found (mg)
Error (mg)
13.70 27.50 41.20
96.30 192.60 289.00
13.73 27.46 41.21
0.03 -0.04
0.01
RESULTS AND DISCUSSION
Analysis A known amount of barium complex was decomposed with a mixture of perchloric acid, sulfuric acid, and nitric acid, and barium contents were determined volumetrically (1.5). Nitrogen was estimated by a modified Kjeldahl procedure (1) and sulfur by Messenger’s method (11). Calculated Found
IV(%I 11.68 11.78
s f%) 6.67 6.72
Ba (%) 14.02 13.98
IR Spectral Data Sulfadimethoxin salicylaldimine gives two bands at 3580 cm-’ and 2600 cm-‘, which may be assigned to intramolecular hydrogen bonding and chelated OH involving N (2, 14). These two bands are absent in barium chelate. A strong band at 1640 cm-’ assignable to C=N stretch (3) of SUDMSA is observed in the chelate at 1660 cm-l. The observed shift obtained in C=N stretch after chelation suggests that azomethine nitrogen is coordinated to the metal ions.
94
JA’N
AND
CHATURVEDI
TABLE
2
(mg)
Foreign ion added (40 mg)
Masking reagent used
Ba(II) estimated (mg)
Error (ms)
1
2
3
4
5
10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Ca(I1) Sr(I1) Mg(IU Sn(IV) RidI) W) ZrO(I1) Cr(III) Ni(I1) Cu(I1) Co(H) Mn(I1) Zn(I1) Cd(H) Pd(I1) MU Fe(II1) As(II1) Sb(II1)
KCN - ”
9.98 9.98 9.98 9.96 9.99 9.98 9.98 9.97 10.02 9.97 9.99 9.98 9.98 9.96 9.98 9.98 9.98 10.02 9.98
-0.02 -0.02 -0.02 -0.04 -0.01 -0.02 PO.02 -0.03 +0.02 -0.03 -0.01 -0.02 -0.02 -0.04 -0.02 -0.02 -0.02 +0.02 -0.02
Ba(II) taken
KCN KCN KCN KCN NH,F NH,F KCN KCN Tartrate Tartrate Tartrate
n Masking reagent not required.
The band at 1275 cm-’ in SUDMSA may be assigned to phenolic C-O stretching in SUDMSA. Similarly the band at 1315 cm-’ in chelate may be assigned to phenolic C-O stretching in chelate and also possibly to combination frequency of M-O bonds and M-N linkages. These observations lead to the following conclusions: (i) In Ba-chelates the azomethine nitrogen has taken part in the coordinate bond formation. As a result of this, the bond order of carbon to the nitrogen link is increased. (ii) Disappearance of hydrogen-bonded -OH in the chelate and high frequency shift of the phenolic C-O stretch are suggestive of M-O bond formation. On the basis of the above data the structure of barium chelate may be represented as:
95 SUMMARY Sulfadimethoxin salicylaldimine (SUDMSA) has been found to be a wide spectrum precipitant of a number of metal ions. The chelates are granular, stable, and quantitatively formed. SUDMSA has been utilized for the gravimetric determination of barium in the presence of Ca(II). Sr(lI), Fe(III), As(II1). Sb(lI1). Cr(II1). Ag(1). Cu(l1). Ni(I1). Co(I1). Mn(II). Cd(II), Zn(II), Hg(I1). Pd(II), Mg(I1). Tl(1). ZrO(II), Sn(IV). The St. of the chelate was confirmed by elemental analysis and IR data.
ACKNOWLEDGMENTS The authors wish to thank CSIR New Delhi for the award of a research fellowship and Roche Product, Ltd., for the supply of sulfadimethoxin.
to P. J.
REFERENCES 1. Ashraf. M.. Semi-micro nitrogen estimation. 7i1/e~rt~115, 555 (1968). 2. Bellamy, L. J.. “The I. R. Spectra of Complex Molecules.” Methuen, London, 1964. 3. Clougherty, L. E., Sousa, J. A.. and Wyman. G. M., C=N stretching frequency in infra-red spectra of aromatic azomethines. J. Or~v. C/re,?r. 22, 462 (1957). 4. Gupta. R. R.. and Kaushal. R., Metal complexes of sulphathiazole salicylaldimine. .I. fndiun Ckrm. Sot. 51, 385-386 (1974). 5. Jam P., and Chaturvedi. K. K., Thermodynamic formation constants of some chelates of sulphadiazine salicylaldimine. J. Inditrrr Cl~crrr. Sot,. 52, 805-806 (197%. 6. Jain. P.. and Chaturvedi, K. K., Spectrophotometric studies on copper complexes of Schiff bases. J. Indiun C'h~tr7. Sk. 52, IX) (1975). 7. Jain. P.. and Chaturvedi, K. K.. Thermodynamic formation constants of metal chelates Chc~m. Sock. 52, 1225 (1975). of sulfadimethoxin salicylaldimine. J. ft1diut7 8. Jain. P., and Chaturvedi. K. K.. Potentiometric studies on complexes of Cu(II), Ni(II), and Co(I1) with sulfamethazine salicylaldimine. J. Inor,?. N~fc~/. C/te/>t. 38, 799-800 (1976). 9. Jain. P., and Chaturvedi. K. K.. Co-ordination complexes of Cu(II), N1(11) and Co(I1) with sulfadimethoxin salicylaldimine. I,rdicln J. Chet~t. (communicated). 10. Mukherjee. A. K., and Ray, P.. Intermetallic complex salts of oxyaldimines with polycyclic rings. J. Intlicirr C‘/wm. Sot 32, 604-608 ( 1955). II. Sudborough. J. J., and Campbell. J. T.. “Practical Organic Chemistr-y,” p. 66. Blackie Sons, Ltd.. London 1949. 12. Tsukamato, T.. and Kennosuke. Y.. Halosalicylaldehyde as a reagent for primary amines. I’N/,I~R(IXII Zas.shi 78, 706-709 (1958): C/rem. Ahstr. 52, 18293b (1958). p. 5766. Takeda Pharmaceutical Industries Ltd.. 13. Tsukamato, T.. “Anil Compounds.” Japan. 1960: Chrnr. 4hstr. 55, 5879f (1961). 14. Weissberger, A., “Techniques of Organic Chemistry. ” Interscience. New York. Vol. 9. p. 394. 1956. 15. Welcher, F. J., “The Analytical Uses of Ethylene Diamine Tetraacetic Acid.” D. Van Nostrand. New) York. 1958.
J”“RNAL
22, 92-95 (1977)
Separation and Gravimetric Determination of Barium Using Sulfadimethoxin Salicylaldimine PRABUDDHA Department
JAIN
of Chemistry,
AND KAMAL Holkar
Received
K.
CHATURVEDI
Science College.
Indore,
India
April 6, 1976
INTRODUCTION
Perusal of literature reveals that condensation products of sulfadiazines with salicylaldehyde and substituted salicylaldehyde are not only good bacteriostatic agents (12, 13), but are also good complexing agents (5-8). Sulfadimethoxin salicylaldimine (SUDMSA) has the system -0-C=C-C=N, similar to many precipitating agents used for a number of transition metal ions. The reagents having such a system have been investigated by a number of workers (4). The present work deals with chelates formation of SUDMSA with Ba(I1). EXPERIMENTAL Chemicals
All chemicals employed were of Analar grade. Reagents
The aqueous stock solution of barium chloride was prepared by dissolving 1 g of BaCl, in a liter of double-distilled water. The contents of barium were determined volumetrically (15) and a stock solution of the 0.001 M concentration was prepared by appropriate dilution. SUDMSA was synthesized by the procedure described earlier (9). A 1% solution of the masking reagents was prepared by dissolving the requisite amount in double-distilled water. Procedure
Barium chloride solution (5 ml, 0.01 M) was diluted to 100 ml and warmed. To the hot solution, a solution of the reagent (a slight excess was used) was added with stirring. The pH of the resulting solution was adjusted to 6.00. The white precipitate of the complex formed settled down on digestion for 30 min on water bath leaving a clear supernatant liquid. The precipitates were filtered through a sintered glass crucible of the porosity G-4 and were washed thoroughly with hot water and finally with 20% alcohol-water solution. The barium complex thus obtained was dried at 115-120°C. and weighed as (C,,H,,O,N,S),Ba. 92 Copyright All richts
@ 1977 by Academic Press. Inc. of renrodrrction in IVY fnrm re*rrurri
93 Separation of Barium from Other Metal Ions With a view to separate barium from the other metal ions, a 14.56 ml (0.01 M) solution of barium chloride was mixed with a known amount of desired foreign metal ions (40 mg) and diluted to 100 ml. A 5-ml portion of 1% masking reagent solution was added and the contents were warmed. To the hot solution, a solution of the reagent (a slight excess was used) was added and the pH was adjusted to 6.0. The complex so formed was allowed to stand on water bath for 30 min. Thus. barium could be separated and precipitated quantitatively in the presence of Ag(I), Mn(II), Cu(II), Ni(II), Co(II), Cd(II), Zn(I1). Hg(II), Pd(II), Ca(II), Sr(I1). Cr(II1). Fe(III), Mg(II), As(III), Sb(III), Sn(IV). Tl(I), and ZrO(II)(Tables 1 & 2).
S. No
0.01 M BaCl, (ml)
I.
10.00
2. 3.
20.00 30.00
Barium taken (mg)
Weight of complex (w)
Barium found (mg)
Error (mg)
13.70 27.50 41.20
96.30 192.60 289.00
13.73 27.46 41.21
0.03 -0.04
0.01
RESULTS AND DISCUSSION
Analysis A known amount of barium complex was decomposed with a mixture of perchloric acid, sulfuric acid, and nitric acid, and barium contents were determined volumetrically (1.5). Nitrogen was estimated by a modified Kjeldahl procedure (1) and sulfur by Messenger’s method (11). Calculated Found
IV(%I 11.68 11.78
s f%) 6.67 6.72
Ba (%) 14.02 13.98
IR Spectral Data Sulfadimethoxin salicylaldimine gives two bands at 3580 cm-’ and 2600 cm-‘, which may be assigned to intramolecular hydrogen bonding and chelated OH involving N (2, 14). These two bands are absent in barium chelate. A strong band at 1640 cm-’ assignable to C=N stretch (3) of SUDMSA is observed in the chelate at 1660 cm-l. The observed shift obtained in C=N stretch after chelation suggests that azomethine nitrogen is coordinated to the metal ions.
94
JA’N
AND
CHATURVEDI
TABLE
2
(mg)
Foreign ion added (40 mg)
Masking reagent used
Ba(II) estimated (mg)
Error (ms)
1
2
3
4
5
10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Ca(I1) Sr(I1) Mg(IU Sn(IV) RidI) W) ZrO(I1) Cr(III) Ni(I1) Cu(I1) Co(H) Mn(I1) Zn(I1) Cd(H) Pd(I1) MU Fe(II1) As(II1) Sb(II1)
KCN - ”
9.98 9.98 9.98 9.96 9.99 9.98 9.98 9.97 10.02 9.97 9.99 9.98 9.98 9.96 9.98 9.98 9.98 10.02 9.98
-0.02 -0.02 -0.02 -0.04 -0.01 -0.02 PO.02 -0.03 +0.02 -0.03 -0.01 -0.02 -0.02 -0.04 -0.02 -0.02 -0.02 +0.02 -0.02
Ba(II) taken
KCN KCN KCN KCN NH,F NH,F KCN KCN Tartrate Tartrate Tartrate
n Masking reagent not required.
The band at 1275 cm-’ in SUDMSA may be assigned to phenolic C-O stretching in SUDMSA. Similarly the band at 1315 cm-’ in chelate may be assigned to phenolic C-O stretching in chelate and also possibly to combination frequency of M-O bonds and M-N linkages. These observations lead to the following conclusions: (i) In Ba-chelates the azomethine nitrogen has taken part in the coordinate bond formation. As a result of this, the bond order of carbon to the nitrogen link is increased. (ii) Disappearance of hydrogen-bonded -OH in the chelate and high frequency shift of the phenolic C-O stretch are suggestive of M-O bond formation. On the basis of the above data the structure of barium chelate may be represented as:
95 SUMMARY Sulfadimethoxin salicylaldimine (SUDMSA) has been found to be a wide spectrum precipitant of a number of metal ions. The chelates are granular, stable, and quantitatively formed. SUDMSA has been utilized for the gravimetric determination of barium in the presence of Ca(II). Sr(lI), Fe(III), As(II1). Sb(lI1). Cr(II1). Ag(1). Cu(l1). Ni(I1). Co(I1). Mn(II). Cd(II), Zn(II), Hg(I1). Pd(II), Mg(I1). Tl(1). ZrO(II), Sn(IV). The St. of the chelate was confirmed by elemental analysis and IR data.
ACKNOWLEDGMENTS The authors wish to thank CSIR New Delhi for the award of a research fellowship and Roche Product, Ltd., for the supply of sulfadimethoxin.
to P. J.
REFERENCES 1. Ashraf. M.. Semi-micro nitrogen estimation. 7i1/e~rt~115, 555 (1968). 2. Bellamy, L. J.. “The I. R. Spectra of Complex Molecules.” Methuen, London, 1964. 3. Clougherty, L. E., Sousa, J. A.. and Wyman. G. M., C=N stretching frequency in infra-red spectra of aromatic azomethines. J. Or~v. C/re,?r. 22, 462 (1957). 4. Gupta. R. R.. and Kaushal. R., Metal complexes of sulphathiazole salicylaldimine. .I. fndiun Ckrm. Sot. 51, 385-386 (1974). 5. Jam P., and Chaturvedi. K. K., Thermodynamic formation constants of some chelates of sulphadiazine salicylaldimine. J. Inditrrr Cl~crrr. Sot,. 52, 805-806 (197%. 6. Jain. P.. and Chaturvedi, K. K., Spectrophotometric studies on copper complexes of Schiff bases. J. Indiun C'h~tr7. Sk. 52, IX) (1975). 7. Jain. P.. and Chaturvedi, K. K.. Thermodynamic formation constants of metal chelates Chc~m. Sock. 52, 1225 (1975). of sulfadimethoxin salicylaldimine. J. ft1diut7 8. Jain. P., and Chaturvedi. K. K.. Potentiometric studies on complexes of Cu(II), Ni(II), and Co(I1) with sulfamethazine salicylaldimine. J. Inor,?. N~fc~/. C/te/>t. 38, 799-800 (1976). 9. Jain. P., and Chaturvedi. K. K.. Co-ordination complexes of Cu(II), N1(11) and Co(I1) with sulfadimethoxin salicylaldimine. I,rdicln J. Chet~t. (communicated). 10. Mukherjee. A. K., and Ray, P.. Intermetallic complex salts of oxyaldimines with polycyclic rings. J. Intlicirr C‘/wm. Sot 32, 604-608 ( 1955). II. Sudborough. J. J., and Campbell. J. T.. “Practical Organic Chemistr-y,” p. 66. Blackie Sons, Ltd.. London 1949. 12. Tsukamato, T.. and Kennosuke. Y.. Halosalicylaldehyde as a reagent for primary amines. I’N/,I~R(IXII Zas.shi 78, 706-709 (1958): C/rem. Ahstr. 52, 18293b (1958). p. 5766. Takeda Pharmaceutical Industries Ltd.. 13. Tsukamato, T.. “Anil Compounds.” Japan. 1960: Chrnr. 4hstr. 55, 5879f (1961). 14. Weissberger, A., “Techniques of Organic Chemistry. ” Interscience. New York. Vol. 9. p. 394. 1956. 15. Welcher, F. J., “The Analytical Uses of Ethylene Diamine Tetraacetic Acid.” D. Van Nostrand. New) York. 1958.