DR. C. A. MAC MUNN ON ENTEROCHLOROPHYLL, AND ALLIED PIGMENTS. 249 
solutions and those just described are noticed. An absolute alcohol solution prepared 
in the usual way gives spectrum 7, Chart II., in a deep layer, and spectrum 8, 
Chart II., in a shallow one. The solution was a brilliant green, with a blood-red 
fluorescence, and its bands read as follows: 1st, A 679‘5 to A 636; 2nd, A 627 to 
A 600; 3rd, A 593 to A 566; 4th, A 551 to A 532; and in a thinner layer: 5th, 
A 486’5 to A 467 ; 6th, A 451 to A 438 (?). 1 found that caustic soda alone certainly 
affected these hands ; that before D could no longer be seen, and the whole spectrum 
appeared as shown in spectrum 9, Chart II.* The band in red had completely 
changed its position, as it now read from A 662'5 to A 627, and blended into the 
second band; 3rd, A 582 to A 560; 4th, A 537 to A 519; moreover the red 
fluorescence was no longer as noticeable as before. The change brought about, with 
regard to the position of the bands, is somewhat similar to that caused by nitric 
acid; thus the alcohol solution of the above chlorophyll on treatment with nitric acid 
gave : 1st band, A 665 to A 640 ; 2nd, A 615'5 to A 593 ; 3rd, A 579 to A 560 ; 4th, 
A 543 to A 519, the fluorescence being also much diminished. I also found that acetic 
acid moved the edge of the principal chlorophyll band towards red , not, as is usually 
stated, towards violet—-a change which is often seen in solutions of enterochlorophyll. 
Thus the darkest part of the band is A 703 to A 665, and then a shading A 665 to 
A 645. t Ammonia diminishes J the red fluorescence. The above results show 
that there is yet much to be learned about the chlorophyll of plants, and that the 
saponification process is not quite as harmless towards chlorophyll as recent writers 
would have us believe. On saponifying and agitating the soap with petroleum-ether 
a yellow solution was obtained, which gave three bands in the violet half of the 
spectrum, spectrum 10, Chart II., the third band being only visible by daylight. This 
third band is not constant; in other similar solutions from grass I failed to see it. 
The two first bands read : A 490'5 to A 470 ; 2nd, A 458 - 5 to A 445 (?). On treating 
the solid residue from this solution with iodine in iodide of potassium it became green, 
with nitric acid dirty green, and with sulphuric acid green and slaty-blue. A 
chloroformic solution of the yellow residue showed three distinct bands, two of which 
read : 1st, A 501 to A 481 ; 2nd, A 467 to A 451 (?). A bisulphide of carbon solution 
showed only two distinct bands : 1st, A 521’5 to A 498‘5 ; 2nd, A 488 to A 470. 
An attempt to obtain the needle-shaped crystals of chlorophyll yellow only partially 
succeeded. 
* It is a remarkable fact that the decomposability of vegetable chlorophyll differs very much in 
different cases. I often failed to bring about this change with caustic soda in similar solutions, which 
also causes precipitation in such solutions. Cf. Dragendorff’s “ Plant Analysis,” 2nd Eng. ed., 1884, 
p. 114, note ; here it is shown that possibly the chlorophyll may exist in different states of com¬ 
bination in plants. 
t Possibly two bands may have been formed ; note the above readings; this appearance also varies very 
much in different cases. I frequently noticed a narrow dark band placed over a lighter one. 
+ The diminution of the fluorescence by alkalies appears to be due to precipitation. 
MDCCCLXXXVI. 2 K 
