Correction - Granulated Fertilizers
1
July 1956 INDUSTRIAL AND ENGINEERING CHEMISTRY 1189 SUMMARY This investigation of the heterogeneous hydrolysis of native cellulose fibers was primarily performed to study structural dif- ferences between the resistant portions of wood and cotton fibers. The heterogeneous hydrolysis of the fibers with constant- boiling hydrochloric acid can be subdivided into an initial rapid process and a subsequent slower first-order reaction which was studied from SOY0 to 15% yields of residual hydrocellulose. The initial fast hydrolysis of both cotton (dewaxed Empire cotton) and wood (chemical grade sulfite pulp from hemlock) fibers in- volves a decomposition of the elementary cellulose fibrils (micelle strings of about 100 A. in width) into shorter rodl’ike fragments (micelles) giving sharper x-ray reflections than the original fibers. The initial hydrolytic attack studied with optical microscopy proceeds preferentially along certain cleavage planes in the fibers, giving irregular coarse fiber fragments. The following slow hydrolysis ofcotton cellulose to yields of 15% does not decrease the osmotic DP, of the hydrocellulose, gives no change in the size of micelles (measured on electron micrographs), and no change in the x-ray reflections. For the wood pulp, o n h e other hand, the slow hydrolysis to 15y0 yield decreases the DP, by about 30%, reduces the width of the micelles by one fourth and increases the width of the x-ray reflections by about 15%. It was observed with the optical microscope that the hydrolysis to low yields of both cotton and wood pulp causes a very marked gradual decrease in the size of the fiber fragments down to about 1 micron. From these results the mechanism of the heterogene- ous hydrolysis of wood and cotton cellulose appears to be dif- ferent. The more resistant cotton cellulose micelles seem to remain unchanged until they disappear by a rapid process, whereas the wood cellulose micelles show a gradual lateral attack during the hydrolysis reaction. This indicates a basic difference in chemical resistance between native wood and cotton cellulose. ACKNOWLEDGMENT The authors are much indebted to J. F. Saeman, Forest Prod- ucts Laboratory, Madison, Wis., for preparing the hydro- cellulose samples used. This investigation has been supported by a research grant from the Swedish Technical Research Coun- cil (Statens Tekniska ForskningsrLd) which is gratefully ac- knowledged. LITERATURE CITED (1) Battista, 0. A., IND. ENG. CHEM., 42, 502 (1950). (2) Dymling, E., Gierts, H. W., Rhnby, B. G., Svensk Papperste’dn. (3) Hartler, N., Samuelson, O., Ibid., 55, 851 (1952). (4) Hermans, P. H., Weidinger, A., J. Polymer Sci. 4, 317 (1949). (5) Hock, C. W., Textile Research J. 20, 141 (1950). (6) Immergut, E. H., Rhnby, B. G., Mark, H. F., Paper presented at the International Symposium on Macromolecular Chemis- try, Milano-Torino, September 1954. 58, 10 (1955). Ricerca Sci. 25 (1955). (7) Jorgensen, L., Acta Chem. Scand. 4, 185,658 (1950). (8) Jorgensen, L., “Studies on the Partial Hydrolysis of Cellulose, (9) Linderot, J., Svenslc Papperstidn. 59, 37 (1956). dissertation, Oslo, Norway, 1950. (IO) Lovell, E. L., Goldschmidt, O., IND. ENG. CHEM. 38,811 (1949). (11) McBurney, L. F., in E. Ott, H. M. Spurlin, and M. W. Grafflin, ed., “Cellulose and Cellulose Derivatives” 2nd ed., part I, chap. I11 C, Interscience, New York, 1954. (12) Madorsky, S. L., J. Polymer Sci. 9, 133 (1952); 11, 491 (1953). (13) Mehta, P. C., Pacsu, E., Textile Research J. 18, 387 (1948); (14) Meller, A., J. Polymer Sci. 4, 619 (1949);10, 213 (1953). (15) Millett, M. A., Moore, W. E., Saeman, J. F., IND. ENG. CREM. (16) Morehead, F. F., Textile Research J. 20, 549 (1950). (17) Nelson, M. L., Conrad, C. M., Ibid., 18, 149 (1948). (18) Nickerson, R. F., IND. ENG. CHEM. 33, 1022 (1941); 34, 85, (19) Nickerson, R. F., Habrle, J. A., Ibid., 37, 1115 (1945). (20) Purves, C. B., in L. E. Wise and E. C. Jahn, ed., “Wood Chem- istry,” 2nd ed., vol. I, pp. 182-205, Reinhold, New York, 1952. 19, 699 (1949). 46, 1493 (1954). 1480 (1942). (21) ROnby, B. G., Acta Chem. Scand. 6, 116,128 (1952). (22) Rhnby, B. G., “Fine Structure and Reactions of Native Cellu- (23) Rollins, M. L., Tripp, V. W., Teztile Research J. 24, 345 (1954). (24) Roseveare, W. E., IND. ENG.CHEM. 44, 168 (1952). (25) Samuelson, O., GrangLrd, G., Jonsson, K., Schramm, K., Svensk Papperstidn. 56, 779 (1953). (26) Sharples, A., J. Polymer Sci. 13, 393 (1954). (27) Simha, R., Trans. N. Y. Acad. Sci. 14, 151 (1952). (28) Vogel, A., J. makromol. Chem. 11, 111 (1953). (29) Zimm, B. H., Myerson, I., J. Am. Chem. SOC. 68, 911 (1946). RBCEIVED for review June 10, 1955. ACCEPTED February 29, 1956. Division of Cellulose Chemistry, 127th ACS Meeting, Cincinnati, Ohio March-April 1955. lose,” dissertation, Uppsala, 1952. ~ ~~ Corrections The editors regret that, in the final printing, the references for both corrections [IND. ENG. CHEM. 48, 797 (April 1956)] were interchanged. Once again, the editors are printing these correc- tions as they should have appeared. In the article entitled “Sizing Pipe for Flow of Cellulose Ace- tate Solutions” [F. L. Symonds, +4. J. Rosenthal, E. H. Shaw, IND. ENQ. CHEM. 47, 2463 (1955)], Equation 10 on page 2464 should read DAp/4L = 32gp(/uD3 In the article entitled, “Stearato Chromic Chloride’’ [R. K. Iler, IND. ENG.CHEM. 46, 766 (1954)], U. S. Patent number in literature cited (6) on page 769 should be U. S. Patent 2,307,045 In the article entitled “Granulated Fertilizers” [H. W. Haines, Jr., Fremont Lange, IND. ENG. CHEM. 48, 966 (1956)], the figure on page 967 should be replaced with the following drawing: U.S. Consumption of Plant Nutrients and Fertilizers (Million Tons) Source USDA I> 20 15 10 5 5 The top line of each shaded area is the actua1:consurnption data In the article entitled “Liquid Propellant Handling, Transfer, and Storage” [P. M. Terlizzi, Howard Strem, IND. ENQ.CHEW 48,774 (1956)], the following correction should be made: On page 776, column 2, the third paragraph, line 4, General Motors Corp. should be changed to read GMC-type canister
Transcript of Correction - Granulated Fertilizers
July 1956 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 1189
SUMMARY
This investigation of the heterogeneous hydrolysis of native cellulose fibers was primarily performed to study structural dif- ferences between the resistant portions of wood and cotton fibers.
The heterogeneous hydrolysis of the fibers with constant- boiling hydrochloric acid can be subdivided into an initial rapid process and a subsequent slower first-order reaction which was studied from SOY0 to 15% yields of residual hydrocellulose. The initial fast hydrolysis of both cotton (dewaxed Empire cotton) and wood (chemical grade sulfite pulp from hemlock) fibers in- volves a decomposition of the elementary cellulose fibrils (micelle strings of about 100 A. in width) into shorter rodl’ike fragments (micelles) giving sharper x-ray reflections than the original fibers. The initial hydrolytic attack studied with optical microscopy proceeds preferentially along certain cleavage planes in the fibers, giving irregular coarse fiber fragments. The following slow hydrolysis ofcotton cellulose to yields of 15% does not decrease the osmotic DP, of the hydrocellulose, gives no change in the size of micelles (measured on electron micrographs), and no change in the x-ray reflections. For the wood pulp, o n h e other hand, the slow hydrolysis to 15y0 yield decreases the DP, by about 30%, reduces the width of the micelles by one fourth and increases the width of the x-ray reflections by about 15%. It was observed with the optical microscope that the hydrolysis to low yields of both cotton and wood pulp causes a very marked gradual decrease in the size of the fiber fragments down to about 1 micron. From these results the mechanism of the heterogene- ous hydrolysis of wood and cotton cellulose appears to be dif- ferent. The more resistant cotton cellulose micelles seem to remain unchanged until they disappear by a rapid process, whereas the wood cellulose micelles show a gradual lateral attack during the hydrolysis reaction. This indicates a basic difference in chemical resistance between native wood and cotton cellulose.
ACKNOWLEDGMENT
The authors are much indebted to J. F. Saeman, Forest Prod- ucts Laboratory, Madison, Wis., for preparing the hydro- cellulose samples used. This investigation has been supported by a research grant from the Swedish Technical Research Coun- cil (Statens Tekniska ForskningsrLd) which is gratefully ac- knowledged.
LITERATURE CITED
(1) Battista, 0. A., IND. ENG. CHEM., 42, 502 (1950). (2) Dymling, E., Gierts, H. W., Rhnby, B. G., Svensk Papperste’dn.
(3) Hartler, N., Samuelson, O., Ibid. , 55, 851 (1952). (4) Hermans, P. H., Weidinger, A., J . Polymer Sci. 4, 317 (1949). (5) Hock, C. W., Text i le Research J . 20, 141 (1950). (6) Immergut, E . H., Rhnby, B. G., Mark, H. F., Paper presented
at the International Symposium on Macromolecular Chemis- try, Milano-Torino, September 1954.
58, 10 (1955).
Ricerca Sci . 25 (1955). (7) Jorgensen, L., Acta Chem. Scand. 4, 185, 658 (1950). (8) Jorgensen, L., “Studies on the Partial Hydrolysis of Cellulose,
(9) Linderot, J., Svenslc Papperstidn. 59, 37 (1956). dissertation, Oslo, Norway, 1950.
(IO) Lovell, E. L., Goldschmidt, O., IND. ENG. CHEM. 38,811 (1949). (11) McBurney, L. F., in E. Ott, H. M. Spurlin, and M. W. Grafflin,
ed., “Cellulose and Cellulose Derivatives” 2nd ed., part I, chap. I11 C, Interscience, New York, 1954.
(12) Madorsky, S. L., J . Polymer Sci. 9, 133 (1952); 11, 491 (1953). (13) Mehta, P. C., Pacsu, E., Textile Research J . 18, 387 (1948);
(14) Meller, A., J . Polymer Sci. 4, 619 (1949); 10, 213 (1953). (15) Millett, M. A., Moore, W. E., Saeman, J. F., IND. ENG. CREM.
(16) Morehead, F. F., Textile Research J. 20, 549 (1950). (17) Nelson, M. L., Conrad, C. M., Ibid., 18, 149 (1948). (18) Nickerson, R. F., IND. ENG. CHEM. 33, 1022 (1941); 34, 85,
(19) Nickerson, R. F., Habrle, J. A., Ibid. , 37, 1115 (1945). (20) Purves, C. B., in L. E. Wise and E. C. Jahn, ed., “Wood Chem-
istry,” 2nd ed., vol. I, pp. 182-205, Reinhold, New Y o r k , 1952.
19, 699 (1949).
46, 1493 (1954).
1480 (1942).
(21) ROnby, B. G., Acta Chem. Scand. 6, 116, 128 (1952). (22) Rhnby, B. G., “Fine Structure and Reactions of Native Cellu-
(23) Rollins, M. L., Tripp, V. W., Tezti le Research J . 24, 345 (1954). (24) Roseveare, W. E., IND. ENG. CHEM. 44, 168 (1952). (25) Samuelson, O., GrangLrd, G., Jonsson, K., Schramm, K.,
Svensk Papperstidn. 56, 779 (1953). (26) Sharples, A., J . Polymer Sci. 13, 393 (1954). (27) Simha, R., Trans. N . Y . Acad. Sci. 14, 151 (1952). (28) Vogel, A., J . makromol. Chem. 11, 111 (1953). (29) Zimm, B. H., Myerson, I., J . Am. Chem. SOC. 68, 911 (1946). RBCEIVED for review June 10, 1955. ACCEPTED February 29, 1956. Division of Cellulose Chemistry, 127th ACS Meeting, Cincinnati, Ohio March-April 1955.
lose,” dissertation, Uppsala, 1952.
~ ~~
Corrections The editors regret that, in the final printing, the references for
both corrections [IND. ENG. CHEM. 48, 797 (April 1956)] were interchanged. Once again, the editors are printing these correc- tions as they should have appeared.
I n the article entitled “Sizing Pipe for Flow of Cellulose Ace- tate Solutions” [F. L. Symonds, +4. J. Rosenthal, E. H. Shaw, IND. ENQ. CHEM. 47, 2463 (1955)], Equation 10 on page 2464 should read
DAp/4L = 32gp(/uD3
In the article entitled, “Stearato Chromic Chloride’’ [R. K. Iler, IND. ENG. CHEM. 46, 766 (1954)], U. S. Patent number in literature cited (6) on page 769 should be
U. S. Patent 2,307,045
In the article entitled “Granulated Fertilizers” [H. W. Haines, Jr., Fremont Lange, IND. ENG. CHEM. 48, 966 (1956)], the figure on page 967 should be replaced with the following drawing:
U.S. Consumption of Plant Nutrients and Fertilizers (Million Tons) Source USDA
I >
20
1 5
10
5
5
The top line of each shaded area is the actua1:consurnption data
In the article entitled “Liquid Propellant Handling, Transfer, and Storage” [P. M. Terlizzi, Howard Strem, IND. ENQ. CHEW 48,774 (1956)], the following correction should be made:
On page 776, column 2, the third paragraph, line 4, General Motors Corp. should be changed to read
GMC-type canister
