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4.

Wislicenus (L. A. 167, 332) obtained the following results :-
Solution, Hydrated Salt.

Anhydrous Salt.
1. c = 16.05. [a]o 6.36 c = 13.98. [a]n 7.30
2. 11.01.

6.36
9.60.

7:29
3.
7:47.
6.83
6:51.

7.83
6.13.
7.41
5:36.

8:49
5.
5.45.
7.34
4:75.

8.43
6.
5.26.
7.60
4:58.

8.73
Solutions 1 and 2 were supersaturated.
Para-lactate of lime, Ca (C3 H; O3)2 + 9 H,0. Lævo-rotatory.
Hydrated salt. C = 7.23. [a]ı 3.87

} Wislicenus.
Anhydrous ,

C = 5:35.

[a]

5.25

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$ 115. Vegetable Acids.
Dextro-tartaric acid, C4H, 06.
See $ 19, p. 47, Arndtsen.
§

The formulæ apply for q = 50 to 95

per

cent.
See also § 26, p. 60, Krecke (For Influence of Temperature).
Water c = 5 to 15. t = 15.

[a]) = + (14:90 – 0.14:3}
.

c) Hesse t = 22.5. [a]o + (15.22 0.14 c) S (L. A. 176, 129). . C = 0.5 to 15. t =

20. [a]p
+ (15.06 – 0.131 c) Landolt (D. C. G.

1873, 1073). The specific rotation of tartaric acid is considerably diminished by the presence of other acids. Biot (Mém. de l'Acad. 16, 229).

Dextro-tartrates. Solutions in water.

The following determinations (Landolt) are for the anhydrous salts. Temperature always at 20°. K. CH,06

0.615 [a]] = + 22.61 Na . H

4.409

23.95 N H4 . Η

1.712

25.65 Li.H

7.998

27.43 11.597

28:48 Na,

9.946

30.85 (NH)

9.433

34.26 Li2

8.305

35.84 K. Na

10.771

29.67 K.NH

10.515

31:11 Na. NH4

9.690

32.65 Mg

8.818

35.86 K. Bo

2-744

51:48 5.488

58.35 Na . Bo

2.538

55.02 5.075

63.48 10.151

71.47 0.563

21.13 Na . As Oy

3.358

20.64 K. Sb 0

7.982

142:76 K. C, H,

11:079

29.91 Bat. C, H,

12.586

25.68

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C =

K2

K”. ASO

-2

6

-2

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26.84

34.96

38.49

4

6

22:04 20.82 31.08 18.52

For sodium tartrate, Na, C4H,08 + 2 H, 0, Hesse (L. A. 176, 122) found :- Water, c = 5 to 15, t = 15. [a]. 27.85

0.17 C. Krecke (Arch. Néerl. VII., 1872) has determined the specific rotation of a few tartrates. At temperatures between 0° and 100°, and for various rays, with concentration c = 20, and the temperature = 25°, he obtained the following results :

[a]. [a]. [a]E [a] [a]s 2 (K, . C, H, 06) + H, O

32.95

39.92 Na, . C, H, 0& + 2 H2O

25.79

32.70 (N H)2 . C, H, Os

37.09

4527. 53.76 K . Na . C4H406 + 4 H, O

27.67 2 (K. SbO .C4H406) + H, 0 (c

5) 111.82 138.66

187.39 218.74 Increase of temperature had little or no effect on the three firstmentioned salts ; Rochelle salt showed increase of specific rotation, but tartar emetic decrease.

Tartrate of ethyl, (C, H;)2. C, H, Og See 33, p. 77.
Lævo-tartaric acid.

Pasteur (A. C. P. [3] 24, 442 ; 28, 56 ; 38, 437) gives the following data, which in part apply to Biot's red ray (see § 18,

4

31.67 43:05 26:49 180.39

22:42

32.08

2

.

4

4

6.

p. 43.

=

Free acid, p = 35-7. t = 17. [a]= – 8:43. (Dextro-rotatory

[ tartaric acid under like conditions gives [a]; = + 8:53. Biot.)

, Lævo-tartrate of ammonia, [a], = – 29.3. The dextro-rotatory salt gives [a], = + 29.0.)

Levo-tartrate of sodium and ammonium, Na.NH.C,H,0. + 4H20. [a]; - 26.0. (The dextro-rotatory salt gives [a]; = + 26.0.)

Lævo-rotatory tartar emetic, [a]; - 156.2. (Dextro-rotatory salt gives [a]; = + 156.2.)

= Lævo-tartrate of lime dissolved in hydrochloric acid (20 grammes tartrate for 63 cubic centimetres of acid, of specific gravity 1:08) gives a decidedly dextro-rotatory solution.

In presence of boracic acid, lævo-tartaric acid behaves exactly as does the dextro-rotatory acid. Biot (A. C. P. [3] 28, 99).

Malic acid, C, H03. Lævo-rotatory.

From mountain-ash berries. A slight lævo-rotation increased by dilution with water as well as by increase of temperature. Water. p = 16.6.

[a].
Ritthausen (Journ. für prakt. Chem.

[2] 5, 354). » p = 32.907. t 10°. [a];

Pasteur (A. C. P. [3] 37, 81).

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The specific rotation is increased considerably by the addition of boracic acid. On the other hand, mineral as well as organic acids diminish it, and may even convert it into dextro-rotation.

MALATES.

.

4

4

5

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+

2

+

4

4

p =

8

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Neutral malate of soda, Na, .C.H. 05. Water. c = 15.976.

t = 22. [a] - 7.64. Landolt. Acid malate of ammonia, NH,.CH, 05. Water.

6.5. 20. [a]. 6.65 Landolt. Water.

C = 23.025. t =
20. [a]s

7.22 Nitric acid of 21° Baumé. p = 26.803. t =

20. [a]j

5.60 after addition of ammonia, lævo-rotatory.

Pasteur Malate of lime, Ca . C4H40+ 3 H, 0.

(A. C. P. Hydrochloric acid of 9.5° Baumé. p 12474. t =

22. [a];

+ 10.88 Ammonia (per cent. ?)

p = 23.506. t =

17. [a]s

4:34 [3] 31, 85). Antimon-ammonium malate, N H. Sb 0.C, H, 05. Water

6.815. t = 17. [a];

+ 115.47 Amides of malic and tartaric acids. Pasteur, (A. C. P.[3] 38, 466).

Glutanic acid, C, H, O. Lævo-rotatory. Water. p = 18.81. [a] 1.98. Ritthausen (Journ. für prakt. Chem. [2] 5, 354).

Glutamic acid, C, H, NOx Dextro-rotatory.
Dilute nitric acid. p = 5.45. t = 18. [a]! = 34.7.

Ritthausen (Journ. für prakt.
Chem. [1] 107, 238).
Aspartic acid, C, H, NO, Dextro-rotatory in acid solutions ;

: lævo-rotatory in alkaline solutions. Dilute nitric acid

P =
4.711. t
20. [a]o

+ 25:16 Ritth. (a) Hydrochloric acid of 9.5° Baumé

p
5.094. t = 22. [a];

= + 27.68

Pasteur
Soda solution containing 4.84 per cent. Na, 0. p = 9.99. [a], 2.22
Ammonia with 10 per cent. N Hz.

4.02.
p =
[a]s 11.67

(6) (a) Ritthausen's preparation from legumin (Journ. für prakt. Chem. [1] 107, 227).

(6) Pasteur's preparation from asparagin (A. C.P. [3] 31, 78).

Asparagin, C, H, N, Oz. Dextro-rotatory in acid solutions ; lævo-rotatory in alkaline. Nitric acid of specific gravity 1:1102 at 22°. p = 11.08. = 22. [a]; = + 35.09. Hydrochloric acid 1.0706 at 23o. p 11.125. t = ? [a];

+ 34.40.

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Soda solution with 4.84 per cent. Na, 0. p = 8.89. t = 8.5. [a]s 7:50. 4.84

P = 17.9.

t = 22. [a]; 7.84. 12.69

р
15.21. t = 22. [a]s

7.31. Ammonia (per cent. ?)

p = 12:72 t =

18. [a]s

11:18.

Pasteur (A. C. P. [3] 31, 75).
Water

p =
1•66. [a]o

6:23. Water and 10 grammes NH, in 100 cub. cent. solution p = 1.66. [a], 10.68.

[a]; 11.38. 10 grammes H CI

p = 1.66. [a]p

+ 37:45, 10 grammes acetic acid in 100 cub. cent. solution p 1.66. Inactive.

Champion and Pellet (C. R. 82, 819). Quinic acid, C, 111206. Lævo-rotatory. Water

c = 2 to 10. t = 15. [a] · 43.9. Alcohol of 80 per cent. by vol.

5.

[a] - 39.2. 1 mol. quinic acid + 1 mol. Na, 0 + Water.

c = 2 [a]. 47.0. Hesse (L. A. 176, 124).

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§ 116. Terpenes, C10 H16. I. Dextro-rotatory Oil of Turpentine, Australene. [The latter name is applied to the preparation obtained by distillation after neutralization by soda solution.]

(a) From Pinus australis and P. Taeda. American or so-called English oil of turpentine.

a; = 135 (crude); 14.6 (rectified). Luboldt. [a]; = 18.6. Guibourt, and Bouchardat.

[a]. = 14:15 at 20°. d = 0.9108. Landolt (ý 31, p. 70). Wiedemann (Pogg. Ann. 82, 222) obtained the following angles of rotation for different rays :

[blocks in formation]

Australene. Distilled at 100° with reduced pressure. Portion I. [a] 24:3. Portion II. [a]; = 21.4.

.

(Boiling-point, 161o.) Berthelot (A. C. P. [3] 40, 5).

(6) From Pinus sylvestris and P. Abies. Russian or so-called German oil of turpentine.

[a]; = 14.6 to 16.3. Luboldt. Australene from Pinus sylvestris, [a]} = 32-4. [a]; = 40.3 with t = 24:5°, (ap = 27:7, d = 0·8547. Boiling-point, 155.5 to 156-5). Flawitzky (D. C. G. 1878, 1846).

Australene from Swedish wood-tar of Pinus sylvestris, [a] = 36-3 (d = 0.8631 at 16o. Boiling-point, 156.5 to 157.5.) Atterberg (D. C. G. 1877, 1203).

D

=

II. Lævo-rotatory turpentine oil. Terebenthene. (Neutralized

and distilled.)

(a) From Pinus Pinaster (P. maritima). French oil of turpentine.

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Commercial oils, a; 18.2, Luboldt; a; 31:1, Gladstone ; a 35.4 to 36.5,

Berthelot; 35.6, Gladstone; 36.5, Gernez; 40·0, Biot; 42:2, Mayer; 43.0, Deville ;
43•4, Soubeiran and Capitaine ; 45:5, Buignet.
For different rays, Wiedemann (A. P. 82, 222) found:-
Lines

B с D E b F G
21.5 23:4 29.3 36.8 38.3 43:6 55.9

a =

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D

Terebenthene. [a]; = 42-3. (Distilled with reduced pressure, at temperatures between 80° and 100°. Boiling-point, 161°.) Berthelot (A. C. P. [3] 40, 5). [a]] 37:01 at 20° (d = 0·8629 at 20°. Boiling-point, 161°). Landolt (§ 30, p. 66). [a]] 40-30 (d = 0·8685 at 10°. Boiling-point, 1569). Riban (A. C. P. [5] 6, 15).

Iso-terebenthene. Obtained by exposing terebenthene for two hours to a temperature of 300°. [a]] = - 9:45 (d = 0·8431 at 20°.

-
Boiling-point, 1759). Riban (A. P. C. [5] 6, 218).

5
(6) From P. Larix. Venetian oil of turpentine.

.
[a];

6:0, Luboldt. [a], 5•24, Guibourt and Bouchardat.
(c) Templin oil. Krummholzoil.
1. From the cones of Pinus picea. Crude : [a];

- 85•2. [a];

= -- 98.8. Rectified: [a]; 92.5. [a]; 107.6. Flückiger, Berthelot (J. B. 1855, 643).

2. From young shoots of Pinus pumilio.[a]; 8.2. Jolly, Buchner (L. A. 116, 328).

By exposure to the air, turpentine oils experience a decrease of rotatory power by oxidation ($ 30), whence probably these discrepancies in the data.' When distilled, the unaltered and more highly rotatory portions are carried over first.

For the alterations of the rotatory power of oil of turpentine at temperatures above boiling-point, see § 16, p. 35.

For information on the rotatory properties of the numerous derivatives of oil of turpentine, as they have been investigated by Deville (A. C. P. [2] 75, 37) and Berthelot (A. C. P. [3] 38, 38; 39, 10; 40, 5), reference must be made to the original memoirs. In the case of most of the solid substances examined the concentrations of

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1 Pinus pumilio is the dwarf pine (Krummholz), a species with recumbent stem found in the Alps and Pyrenees.--D.C.R.

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