UNIFICATION O F REDUCING SUGAR METHODS
541
izes the wood. A n extraction of some of the shavings with alcohol yielded some resinous matter, but other solvents failed to remove appreciable amounts of soluble constituents. Some six kilos of shavings of the dry wood were then treated with steam till about fifty liters of distillate had been obtained. T h e latter was turbid and retained the peculiar odor of the wood. O n standing, no oil separated, but on shaking with petroleutn ether and allowing the latter to evaporate some two grams of white crystals, which possessed the odor of the wood in a marked degree, were obtained. Recrystallization of these gave a pure white compound, which melted a t 80". I t is soluble in a great variety of organic solvents, but does not crystallize readily. A single combustion gave C = 73.23, H = 7.72. T h e molecular weight obtained by the freezing point method using glacial acetic acid as solvent was 157. Apparently the formula of the compound is C,,H120,. The small amount of material available made further study of it impracticable. UNIVERSITY O F CALIFORNIA,
BERKELEY,Jan. 14, 1 9 7 .
[CONTRIBUTION F R O M THE C O X T R A C T S LABORATORY, BUREAU O F CHEMISTRY PUBLISHED BY PERMISSION OF THE SECRETARY OF AGRICULTURE. ]
T H E UNIFICATION OF REDUCING SUGAR METHODS. H. WALKER. Received Jan. 21,1907.
BY P E R C Y
Munson and Walker have recently published' uniform methods and tables for the determination of d-glucose and invert sugar alone, and invert sugar when mixed with sucrose. The authors hoped to take up the study of maltose and lactose. It is regretted that hJr. Munson was unable to continue the work, and the writer, therefore, undertook to complete the work alone. Commercial lactose was repeatedly recrystallized by dissolving in hot water and pouring into alcohol with constant stirring. The fine crystals were dried at first by drawing air over them for three days, and then dried for five days over calcium chloride. Von Lippman2 states that lactose prepared in this manner has the formula, gC,,H,,O,, 2H,O. The product obtained, however, had a composition represented by the formula, C,,H,O,, $H,O. A water determination made according to the method used by Brown, Morris and Miller3 gave 2.43 per cent. This determination was made as follows : The powdered lactose was placed in a small flask connected by a T tube with another small flask containing P,O,, and the remaining limb of the tube connected with an exhaust pump. T h e system was exhausted and the flask containing the lactose kept at 30" for two hours, cooled to room tem-
+
This Journal, 28, 663 (1906). Die Chemie der Zuckerarten, 3 Auflage-1526. J. Chem. SOC.Trans., 71., 76.
+
PERCY H. W'ALKEK
542
perature, and weighed. It had not changed in weight, proving the ahsence of moisture. T h e apparatus was again connected up, exhausted, the flask containing the lactose placed in a paraffin bath at So0, kept at that temperature for one hour, then heated slo\vly to 1303, kept at that teniperature for one hour, cooled and iveighed. The product was still perfectly white ; but on heating for another hour at 14oC,the powder became somewhat tinged with brown. Carbon determinations were macle yielding 40.80 per cent. and 40.98 per cciit., theory being 41.02 per cent. The specific rotation of the lactose was j2.93". T h e maltose used xyas prepared by recrystallizing Nerck's C.P. maltose three times, and drying below 80" iiz zaczio. This gave a specific rotation of 130.48", corresponding to I 37.2 for the anhydrous maltose, which showed it to be a very pure preparation. Some of the same crucibles used in the former work were used in weighing the cuprous oxide, and the method of manipulation previously described was followed. No difficulty lias encountered in getting concordant results with lactose by the tIvo-minute boiling, and this method can be relied upon to give as accurate results as the ordinary method of boiling six minutes. As in the previous work, blanks were riiii each day aiid correctioiis applied to all weighings. In Table I the blanks of each set of determinations a r e given, TABLEI. Number of Set, I
Individual blanks mgs.
0.7
Average mgs.
0.4
0.0
2
0.0
-0.4
~--0.s 3 4 5
0.0
0.0
0.4 1.6 0.6 0.8
1.0
0.7
6
0.3 1.0
0.6
7
0.5
8
0.4 0.6 0.6 0.2
0.4
9
0.4 4 . 2
0. I
UNIFICATION O F REDUCING SUGAR METHODS
543
TABLE11. Reducing Sugar nigs. 20
40
60 80
Lactose C d b O i i % H20 mgs. c u o o found accepted average.
33.2
32.8 62.9 63.4 92.2 93.6 123.8 124.0
33.0 63.2 92.9 123.9
IO0
154.4 153.8
154.1
I20
180.2
180.6
181.0
140 I60 I 80
200 220
240
260
280
210.2
211.2 239.4 239.4 ~65.7~ 268.4 268.I 267.6 296.4 297.8 327.0 326.6
210.7 239.4 268.0
297.I 326.8
355.2 356.9 384.2 384* 6
356.1
412.4~ 414.6 413.1 413.9 443.6 442.6 470.4 470.1
413.9
384.4
443.1
470.3
Maltose Ci?HznOiiH@ mgs. CugO found accepted average.
26.7 26.5 51.7 50.7 75.3
73.9 98.5 97.7 122.9 122.3 145.6 147.0 170.4 170.8 192.0 193.2 216.4 217.2
26.6 51.2
74.7 98.I 122.6 146.3 I 70.6
192.6 216.8
243.0 242.6 266.4 ~68.4~ 268.3* 266.7 290.0 289.4 312.6* 315.0 315.1 3'4. I 340.4 340.2
242.8
362.4 362.4 388.2 387.6
362.4
411.9
411.7
411.5 435.9 434.9 458.2 458.5 481.3 481.7
266.6
289.7 314.7
340.3
387.9
435.4 458.4 481.5
544
P E R C Y H . WALKER
Table II gives the corrected weights of cuprous oxide found for v a r l ing. u eights of the sugars. T h e first column gives tlie iiuiiiber of milligrams of sugar taken, the second and fourth columns give the milligrams of cuprous oxide found, and tlie third and fifth colmiiiis give tlie average results accepted. T h e starred values in the second a i d fourth columns were discarded in taking tlie averages. E>-talcing x = reducing sugar, and J. = cuprous oxide, the relation between the two may be expressed by the equation : y = a -k bx $- cx'. T h e values of a, b, and c can be calculated by the method of least squares from the determined values. Taking the accepted values for lactose 11-e get the following: a: 4.17j9 b = 1.148697 c = 0.0ooo~. Taking the accepted values for maltose we get tlie following: a = 2.5795
b = 1.19694 c = 0.0000~06. By substituting these values in the above equation we can calculate the values distributing any experimental errors over the whole range. In Table 111 are given in parallel columns tlie found and calculated values of Cu,O for each point determined. T h e agreement of values determined and calculated is good, the maximum variation being 2.1milligrams. 111.
?'.ABLE
>Ialto?e
Lactose blilligranis Sugar 20
40
60 so I00 I20
'40 I 60 I so 2ix) 220
240
2 60 2SO
300 320
340 360 380 400
C1?H9~Oj1%H?O Milligrams C n 2 3
found
33.0 63.2 92.9 123.9 '54.1 I Yo. 6 210.7 239.4 26S.o 297. I 326.8 356.1 384.4 413.9
443. I 470.3
calculated
33.9 63.5 93. I 122.6 152.0
c19H~>o11H:o
difference
26.6
26.5
-0.
I
-1
51.2
jd.j
-0.
j
0.3
- 0.2
-1.3 -2.
I
1S1.3
-i-o.7 -0.
327.0
I
-0.4 +I.O
-0.9 --0.2
442.2
-0.2 -0.3 -0.4 -0.9
470.8
- - 0 .j
384.7
313.5
diliereiice
fo.9
210.6 2393 269.0 298.0 355.9
Milligrams CusO found calculated
74.7 9s. I 122.6 Id6.3 170.6 192.6 216.8 242.3 266.6 259.7 314.7 340.3 362.4 387.9 411.7 435.4 458.4 4bI.5
74.4
-0.3
93.4
-0.3
122.4
-0.2
146.4
I 70.4
19.3.4 21S.4 242.4
266.4 290.5 3'4.5 3j5.6
362.6 386.7
410.8
434.9 '159 0 4s3. I
4-0. I -0.2
7-1,5
f1.6 -0.4 -0.2
+0.8
--0.2 -1.7 -0.2 -1.2
-0.9 -0.5 -0.6 ~ 1 . 6
UNIFICATION O F REDUCING SUGAR METHODS Milligrams Milligrams Cuprous Copper Oxide (Cu20) (Cu) IO
I1 I2
'3 I4 15 16
17 I8 19 20
21 22
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
42 43 44 45 46 47 48 49 50 51
52 53 54 55 56 57 58
8.9 9.8 10.7 11.5 12.4 13.3 14.2 15.1 16.0 16.9 17.8 18.7 19.5
Milligrams Milligrams hlilligranis Lactose Milligrams Lactose Maltose Milligrams (C1?Hp2011) Lactose (C1?H??OllH20j(Cl2H2?Ol1) Maltose (Ci?H??Oii%H?O) (C19Hz?OiiH?Oj
3.8 A.5
5. I 5.8 6.4 7. I 7.7 8.4 9. I 9.7 10.4 11.0
20.4
11.7 12.3
21.3
13.0
22.2
13.6 14.3
23. I 24.0 24.9 25.8 26.6 27.5 28.4 29.3 30.2 31.1 32.0 32.9 33.8 34.6 35.5 36.4 37.3 38.2 39.1 40.0 40.9 41.7 42.6 43.5 44.4 45.3 46.2 47.1 48.0 48.9 49.7 50.6 51.5
5 45
15.0 I j.6
16.3 16.9 17.6 18.2 18.9 19.5 20.2
20.9 21.5
3.9 4.6 5.3 5.9 6.6 7.3 8.0
s. 2
5.8 9.5
10.0
10.2
10.6 11.3 12.0 12.7 13.3
10.9 I 1.6 12.3
14.0
14.7 15.3 16.0 16.7 17.4 IS.0 18.7 19.4 20. I
20.7 21.4 22. I
22.8
22.8 23.5 24. I
23.4 24. I 24.8 25.4 26. I 26.8 27.5 28. I 28.8 29.5
25.4 26.1 26.8 27.4
2s. I
28.7 29.4 30.0 30.7 31:3 32.0 32.6 33.3 33.9 34.6 35.2
4.7 5.4 6. I 6.8 7.5
8.6 9.3
22.2
24.8
4.0
30. I
30.8 31.5 32.1 32.8 33.5 34.1 34.5 35.5 36. I
13.0
13.7 14.4 15. I 15.7 16.4 17.1 17.8 18.j 19.2 19.9 20.6 21.3 22.0
22.7 23.3 24.0 24.7 25.4 26. I 26.8 27.5 28.2 28.8 29.5 30.2 30.9 31.6 32.3 33.0 33.6 34.3 35.0 35.7 36.4 37.1
5.9 6.7 7.5 5.3 9. I 9.9 10.6 11.4 12.2
6.2 7.0 7.9
5.7
95 10.4 11.2
12.0 12.9
13.0 13.8 14.6 15.4 16.2 I 7.0 17.S 1S.6 19.4
16.2 17.1 '7.9 18.7 19.6 20.4
20.2
21.2
13.7
14.6 15.4
21.0
22. I
21.8 22.6 23.3 24. I 24.9 25.7 26.5 27.3 28. I 25.9 29.7 30.5
22.9 23.7 24.6 25.4 26.2 27.1 27.9 28.7 29.6 30.4 31.3 32.1 32.9 33.5 34.6 35.4 36.3 37.1 37.9 38.5 39.6 40.4 41.3 42.1 42.9 43.8 44.6 45.4 46.3
31.3
32. I 32.9 33.7 34.4 35.2 36.0 36.8 37.6 38.4 39.2 40.0 40.8 41.6 42.4 43.2 44.0
P E R C Y H. W A L K E R
546 Milligrams Milligrams Cuprous Copper Oxide (CugO) (Cu)
59 60 61 62 63 64 65 66 67 65 69 70
52.4 53.3 54.2 55.I 56.0 56.8 57.7 5S.6
7s
59.5 60.4 61.3 62.2 63.1 64.0 64.8 65. 7 66.6 67.5 6S.4 69.3
79 so
71.1
71
72 -I1
I3
74 75
76 77
SI 82 83
84 85 56
70.2
iI.9 72,s
73.7 74.6 i5.5 i6.4
Si
”-
ss
7s.2
89 90 9‘ 92 93 94 95 96 9i 9s 99
79. I i9.9
I co I 0I IO3
/1.3
s0.s SI.7 S2.6 s3.5 84.4 Sj.3 S6.2
s;. I
s7.9 h5.S s9.7 90.6
I 06
0I.j 92.4 cJ3.3 94.2
107
(,!‘.O
103
104 10.5
Milligrams Milligrams 3Iilligrams Lactose Milligrams Lactose Maltose Milligrams (C12H1z011) Lactose (CI?Hz?OIIHIO) (C1Zhl?2011) Maltose (CnH?zOii%Hd3) (Ci?Hz?OiiH?O)
35.9 36.5 37.2
36.5
37.i
3i.5 3S.2
.iS.4
3s.s
37.8 38.5 39.2 393 40.5
39.5 40.2 40.9 41.6
41.1
42.2
4r.S 42.5 43.’ 43,s 44.4 45. I 45.7 46.4 47.0 47.7 48.4 49.0 49.7 50.3 51.0 51.6 52.3 52.9 53.6 54.3 54.9 55.6 56.2 56.9
42.9 43.6 44.3 44.9 45.6 46.3 47.0 47.6 4s.3 49.0 49.6 50.3 51.0
j1.6 52.3 53.0 53.7
54.3 55.0
55.7 56.4 57.0
57.i 5S.4
5i.5
59.0
58.2
59.7
js.s 59,s 60.2 60.8 61.5 62. I 62.8 63.4
64.I 64.7 65.4
66.I 66.j 67.1
60.4 61.1 61.7 62.4 63, I 6j.5 64.1
39. I 39.8 40.5 41.2 41.9 42.6 43.3 44.0
44.7 45.4 46. I 46,s 1i.5 43.2 48.8
49.5 50.2 50.9 51.6 52.3 jj.0
53.i
54.4 55.0 55.7 56.4 57. I 5i.S
9.5 59.2 59.9 60.6 6:.3 61.9 62.6 63. 3
64.0 64.7 65.4 66. I
44.8 45.6 46.3
47. I
45.0
53.5 54.3
48. 5 49.6 50.5 51.3 52.1 53.0 53.8 54.6 55.5 56.3 57. I
jj. I
j5.0
55.9 56. i
55.8 59.6 60.5 61.3 62. I 63.0 6j.5 64.6 65.5 66.3 67. I 65.0 65.8 69.7
47.1
47.9 48.7 49.5 50.3 51.1
51.9 52.7
57.5 5S.2
59.0 $9.8 60.6 61.4 62.2 63.0 63,s 64.6 65.4 66.2 6j.o
10.5
67.8
71.3
6s.5 69.3
72.2
71 I.
I
70.9 71.7 72.5
73.0 73,5
74.i 75.5
16.3
73.3 74. I
7;. 2
x.9
75.8 19.7
75.7
j6.5
-- ..> .
j5.0
YO. j
6j.I
66.5
7s. I
51.j 52.2
65.8 66.4 07. I 07.8
67.j
78.8
83.0
6P. 1
79.6
5~7.5
80.4
P4.7
(le
s
i ,
!liJ..?
:iI ,?
ST,.;
68.5
70.2
$0.3
6rJ. 1
;o.rj
F2.c $2.8
8;.2
U N I F I C A T I O N OF REDUCING SUGAR METHODS
547
Milligrams Milligrams Milligrams Milligrams Milligrams Cuprous Copper Lactose Milligrams Lactose Maltose Milligrams Oxide (CuzO) (Cu) (C~Hg2011) Lactose (CIgHg~O1lHeO) (CIgHIIOII) Maltose (CIZH ~ ? O I I % He0 ) (CIZHEOIIH@)
95.9 96.8 97.7 98.6 99.5 100.4
101.3 102.2
103.0 103.9 104.8 105.7 106.6 107.5
108.4 109.3 110.1 111.0
111.9 I 12.8
113.7 I 14.6 I 15.5 I 16.4 117.3 118.1 119.0 119.9 120.8 121.7 122.6 123.5 124.4 125.2 I 26. I 127.0
127.9 128.8 129.7 I 30.6 131.5 132.4 133.2 134.I 135.0 135.9 136.8 137.7 138.6
68.0 68.7 69.3 70.0 70.6 71.3 71.9 72.6 73.2 73.9 74.5 75.2 75.8 76.5 77.1
77.8 78.5 79.1 79.8
69.8 70.5 71.1
71.8 72.5 73.1 733 74.5 75.2
75.8 76.5 77 . 2 77.8 78.5 79.2 79.9
80.j
71.6 72.3 73.0 73.6 74.3 75.0 75.7 76.4 77.1
90.0
77.8 78.5 79. I 79.8 80.5
90.7 91.5 92.3 93.1 93.9 94.7 95.5 96.3 97. I 97.9 99.4
86.0 85.7
100.2
105.5
101.0
87.4
101.8 102.6 103.4 104.2
106.4 107.2
100.0
98.1
100.7
101.9 102.6 103.3
98.8 99.4
101.4
104.0
102.0
104.7
88.3 89.0 89.6 90.3 90.9 91.6 92.2 92.9 93.5 94.2 94.8 95.5
96.2
98.0
98.7
96.8
87.0 87.7
89.7 90.5 91.3 92.2 93.0 93.9 94.7 95.5 96.4 97.2
84.7 85.4
97.5
81.7 82.4 83.1 83.7 81.4 85.0 85.7 86.3
88.0 88.8
98.9 99.7 100.5 101.4 102.2 103.0 103.9 104.7
81.2 81.9 82.6 83.3 84.0
81.2 81.9 82.5 83.2 83.9 84.6 8j.2 85.9 86.6 87.3 87.9 88.6 89.3 90.0 90.6 91.3 92.0 92.6 93.3 94.0 947 95.3 95.0 96.7 97.3 98.0 98.7 99.3
80.4 81.1
83.6 84.4 85.2 86.0 86.8 87.6 88.4 89.2
88.I 88.8 89.5 90.2 90.9 91.6 92.3 93.0 93.6 94.3 95.0 95.7 96.4 97.1
105.0
105.8 106.6 107.4 Io8.2
108.0 rc8.9 109.7 110.5 111.4 112.2
113.0 113.9 114.7
97.8
109.0 109.8 110.5 111.3 112.1 112.9 113.7
98.4
114.5
99.I
115.3 116.1 116.9
120.5 121.4
99.8 100.j 101.2
117.7 I 18.j
119.3 120.0
120.8 121.6
115.5
116.4 117.2
118.0 118.9 119.7
122.2
123.0 123.9 124.7 125.5 I 26.4 127.2 128.0
548
PERCY H. W A L K E R
JIillierame Milligrams Milligrams >Iilligrains Milligrams 3lilligrams Lactose hlaltose Milligrains Copper Lactose Lactose ( C 1 ~ I I ~ ~ O 1 l H ? O ) ( C I ~ Maltose H~~O1l) (Cu) (ClrH??On) (CI?H~:OI~$~?H&) (CI?H~.OII€I:O) 100.1 102.j l0.;.
