摘要:

GRAHAM ON CAPILLARY LIQUID TRANSPIRATION ETC. 427 BY TEOMAS GBAHAM,F.R.S. Master of the Mint. [From the Philoeophial Ihserctions,18623 TEE pwsage of liquids under pre~anrethrough a capille tube ia here spoken of ag capillary liquid transpiration in accordance with the analogy of gaseous trampiration. The uubject owea the development whlch it haa already acquired chiefly to the inve&i.. gations of the late Dr. Poiseuille.* The precision of the results * MBm. &wane Etxmp ix. 433 ;Ann. Ch.Php [S] vi'i. and xxi. 428 GRAHAM ON CAPILLARY LiQUID TRANSPIRATION attainable by the mode of experimenting pursued &by that physicist has beeu remarked on by every one who has foilowed him in the inquiry. The observations on this subject which we owe to M.Poiseuille and other inquirers are very numerous but have not so far 8s I am aware been connected hitherto with arly speculative views of the chemical or molecular constitution of liquids. The isolated discovery of M. Poiseuille that diluted alcohol has a point of maximum retardation coinciding with the degree of dilution at which the greatest condensation of the mixed liquids occurs appears to offer a starting point for new inquiries. The same result may be otherwise expressed by saying that the definite compound of 1equivalent of alcohol with 6 equivalentsof water C,H60 +6HO* is more retarded than alcohol containing either a greater or a smaller proportion of water. The rate of transpiration appears here to depend upon chemical composition and to afford an indication of it.A new physid property may thus become available for the determination of the chemical constitution of substances. Methylic alcohol being found to exhibit the same remarkable feature in its transpiration although the 6-hydrate of that alcohol is not distinguished by estrsordinary condensation of volume the inquiry was extended to the hydrated acitla. The results obtained with the latter substances give a certain degree of generality to the relation subsisting between the transpirability and chemical cpmposition of liquids. The apparatus employed was very similar to that of M. Poiseuille. It consisted of a small but rather stout glass bulb A (see figure) about two-thirds of an iuch in diameter having a capacity of from 4 to 8 cub.cent. blown upon a thick glass tube with a bore of about 2 millimetres. A scratch (c) was made upon the glaas tube above and another (d) below the bulb to indicate the available capacity of the instrument. The lower tube was bent at a right angle to the upper and a fine capillary tube B from 3 to 4 inches in length was sealed to the curved extremity of the tube. The bulb and capillary were alwayshheld immersed in a vessel of water during the experiment in order to secure uniformity of temperature. The force employed to impel the liquid through the capillary was the weight of one atmosphere of Halving tlic equivalent of a?eohoi,the hydratc of greatest retardation becomes C,HaO + 3HO. which the level of the liquid in the bulb took to fall from the mark c to themark d.This time varied from about 300 to 900 seconds in different liquids. In successive experiments made upon the same observation did not i I 1 j/ I!- g 480 QICAHAJI ON CAPILLAEY LIQUID TRANSPIRATION Nitric Acid. A bulb provided with s'capillary tube distinguished as capUay C was used in the transpiration of nitric acid and of several other liquids. The dimensions of this bulb C were m follows :-Capacity of bulb 8.075 cub. cent.; length of capillary tube 28 millims.; diameter of bore 0.0942 millim. The time of pamage of water through the tube under the pressure of one atmosphere and at the fixed temperature of 20° wits 348 seconds. The time of the passage of the most highly concentrated nitric acid through the same capillary was found to be 344.5 seconds or slightly less than the time of water.This is the protohydrate of nitric acid HO.NO or NHO,. With the addition of water to the acid the transpiration of equal volumes of liquid becomes gradually slower ; till as much as three additional cquivalents of water were added when the transpiration-time rose to its maximum 732 seconds. The last hydrate is the well-known definite compound NHO + 3H0 having the specific gravity 14 and possessing the highest boiling point of any compour:d of nitric acid and water. Diluted beyond this point nitric acid hcgins to pass more fieely and the tran- spiration-time approaclies again to that of water. With the addition of twice its weiglit of water or about 7 equivalents the acid passed through the capillary in 472 seconds.The experimeritv made upon nitric acid are recorded in the following Table. It will be observed that the retardation is considerable for a certain distance on both sides of the maximum point. No unusual retardation appears to occur with the pro- portions of water correspondiog to 2 and 4 equivalents. The specific gravity of the acid liquid is added in the last column of the Table whenever that property was observed. IN IIELATfON TO CHEMICAL COMPOSITION. 431 TABLE 1.-Transpiration of Nitric Acid at 20"C. by Capillary C,* (Tmnspiration-time of water 348 seconds.) Water added to 100 acid Water per Transpiration-time.spec. grv. (NHo6)* cent. In seconds. Water = 1. at 15'. 0 0 344.5 0.9899 1.6046 26.47 20.38 692 1.9885 1'4359 28-56 . 2 eqs. HO 2 1 -48 705 20268 30 23'07 712 2.0469 40 28-50 725 2.0835 42.86,. 3 eqe. HO 29.99 732 2.1034 1-3978 46 31.03 730 2'0977 60 3333 728.5 2.0919 1.3816 65 35.48 718 2'0632 67.12.. 4 eqa HO 36.35 712 2,0459 60 37-50 709.5 2.0367 1.8698 70 41.17 683 1.9626 13407 80 44.44 6G1 1,8994 1.3239 90 47.36 635.5 1.8261 100 50.00 593 1.7040 1.2943 200 66.66 452 1.3563 It appears then that a certain hydrate of nitric acid is marked out by its low transpirability so distinctly that nitric acid could be identified by that physical property. Such a property may prove to be typical of a class of acids to which nitric acid belongs.The hydration of nitric acid probably advances by three equiva- lents at a time NH06+3H0 as in the maghesian nitrates NMO + 3HO + 3HO. The transpiration of the assumed second hydrate of nitric acid mas not made the subject of experimeat. A certain steadiness is observed in the transpiration of this acid on either side of the point of maximum retardation. * In the following tables the particular capillary employed is in each case designated by a particular letter. Capillary C which was more employed than any other became reduced in length during the course of the experiments the end being ground off on several occasions 0x1account of the choking of the tube. This capillary is then described as C shortened. It did not seem requisite to give in every cam the dilnenaions of the bulb and capillary tube as all the experiments were conducted on the same plan and the transpiration of water is in every cwe given aa a standard of comparison.Direct experiments were also made which proved that the transpiration-timed were sensibly inversely proportional to the effective pressure applied to the liquid as found by Poiseuille ; which indicates that the capillaries offered sufficient resistance to the passage of the liquid. 482 GRAHAM ON CAPILLARY LIQUID TRANSPIRATION Sulplruric Acid. TABLE 11.-Transpiration of Sulyhuric Acid at 20° by Capillary G. (Trsnspiration-time of water 109 seconds.) Watcr added to 100 acid Water per Transpiration-time. -Spea. gn.. (SHW cent. ~ ~~ In seconds.Water = 1. at 16". 0 0 2360 21.6514 1.845~ 2.5 2-43 2412 22.1284 1.8398 6 4-76 2451 22.4862 1.8346 10 9'09 2516 23.0825 1-8120 12.5 11'11 2548 23.3761 1.7976 15 13-04 2587 23.7340 moo 17-5 1489 2591 23%'06 18-36,. 1q.HO 15-15 2466 29.6238 11590 20 16.86 2898 22.0000 1-7473 30 28.07 1623 13.9724 1.6700 86-78.. 2 eqs. HO 2686 1189 10.9090 1'6835 40 28-50 105% 9.6880 1'6146 50 33-33 810 7.4302 1*5600 60 37.50 626 5.7431 1'5118 70 41'17 635 4.9082 80 44'44 450 4.1284 10'0 60'00 382 3-5046 120 54-54 333 3-0458 140 68-33 290 2.6605 160 61'53 260 2.3889 180 64-28 241 2.2110 200 66.66 227 2.0825 The transpiration of sulyhuric acid is very slow being-twenty-four times lea rapid than that of water as might be expected from the viscous quality of the acid fluid.It is surprising however that the first additions of water do not promote the tran- spiration although they lessen in a sensible degree the viscosity of the liquid. The transpiration-time increases from 2,360 to 2,591 seconds and then attains the maximum when 17*5parts of water have been added to 100 parts of oil of vitriQ1. The proportion of water named approacbes closely to one equivalent (18.36 parts). Indeed it is quite possible that the acid mixture which exhibits the least transpirability might have contained a full equivalent of water for a portion of aqueous vapour may have been absorbed from the air during the process of filling the bulb. That the crystallisable hydrate of sulpburic acid SHO +HO is the liquid IN RELATION TO CHEMXCAL UOMPOSXTION 433 of least transpirlrbility is I believe the proper iuference from these observations.With itibreasiug proportions of water the transpiration-time rapidly diminishes till the time is reduced to 227 seconds in a mixture of oil of vitriol with twice its weight of water. A more minute examination than hpra been attempted would be required to show whether the existence of other definite hydrates of sulphuric acid may be indicated by a perceptible rctardatiou in the time of transpiration. Acetic Acid. TABLE III.-Trwpiration of Acetic Acid at 20° by Capillary C. (Transpiration-time of water 348 seconds.) ~ Transpiration4ime. Water per cent.. In seconda Water = 1.~~~ ~ 0.8 0.8 445.9 19801 15 .. 1 eq. HO 20 13-01 16-66 890 921.5 25674 2-6480 1-07ati 1.0742 25 20.00 931 2.6763 27-6 21.66 933 2.6810 30.. 2 eqa. HO 82.5 23.07 24.62 941 934 2.7040 2'6839 1.0762 1.0746 35 25-92 928 2.6666 40 28.50 912 2.6207 45 31.04 895 2.6718 50 33.33 882 2.tia44 1.0720 60.. 4 eqe. HO 90.. 6 eqs. HO 37.50 47m 862 769 24482 2.2098 1.070 The glacial acetic acid made use of in ;hew experiments still retained 043 per cent. of water. Its transpiration-time wm 446.5 seconds. With the addition of 1equivalent of water the time roge to 890 seconds; and with 2 equivalents of water to 941 seconds when it attained ite maximum. This last is the characterktk hydrate of acetic acid C4H40 + 2H0. It is marked out with great precision in theee transpiration experimenta.The times rise very gradually on either aide and appear to culminate exactly rrt that point. It ia ale0 the compound of water and acetic acid of maximum density as ie well-known. The trampiration-time of the hydrate referred to is m much a8 2.7 timeslonger than that 434 GllhIiA31 ON CAPILtAItY LIQUID THANSPIKh'f1ON of pure watcr. With ci equivalents of wtcr acetic acid is still transpired 0.02 tinics mow slowly than water. lh/fyric-Acid. TABLElV.-Trmspiration of Butyric hcid C,H,O, at ZOO by Capillary C shortened. Transpiration-time of water 290 seconds.) Water added to 100 acid Water,per spec.grav. (CJHSO,!. cent. In seconds. Water = 1. at 16". 0 0 454 1.565 a9740 10.22,. 1 eq.HO 9.27 828 2.856 *9901 20.45 . . 2 eqs. HO 16 98 951 3.2'19 a9975 30.67.. 3 eqs. HO 23'47 969 3.341 35-69.. 4.8 eqs. HO 27.95 S63 2.975 111 transpiralility of its hydrates burytic acid presents a con-siderable analogy to acetic acid as might be expected from the rotation of these acids in compositiou. The time of thcacid (C,H804) is 1.565 referred to that of water as 1 and it rises to 2,855 bg the addition of 1equivalent of watcr. By a second equivalent of water the time is increased to 3.279. Herc however the progression does not immediately twn as with acetic acid but the time rises to 3.341 with 3 equivalents of water. With 3.8 equivalents of water the time is 2,975 and Iias accordingly very sensibly receded the maximum point being passed.It is coiiceivable that tlic relation to acetic acid is slightly modified in butyric acid by the interference of some other physical property such as unctuosity that is unequally developed iii the two acids. Vuleriniiic Acid The hydration of this acid cannot be carried beyond 2 equiva-lents but up to that point the transpiratioii is retarded by every addition of water as in acetic and butyric acids. While the basic hydrate (C,,H,,O,) is transpired in 2.155 times the watep period the time increases to 3.634 with 1 equivalent of water added and to 3.839 with 2equivalents. IN RELATION TO CHEMICAL COMPOSITION. 485 TABLEV.-Trmspiratiou of Vrtlerianic Acid at 20°C by Capillary C shortened. (Transpiratioidme of water 290 seconds.) I I I mvm Water added to 100 acid Water per Transpimtion'time' spec* at 15'.1 1 (Ci,HioOJ)* cent* In seconds. I Water = I. Formic Acid. Formic acid appears to diverge considerably from the other members of the acetic acid series in certain physical and chemical characters. While the acetic hydrate is lighter than water and is increased in density by the addition of water the formic hydrate has il higher density than water and has its density uniformly lowercd by dilution as will be seen in the Table which follows. The transpiration-time of formic acid in a concentrated state is also highest and diminishes with dilution in the same regular manner as the density showing no evidence of the acetic maximum at the point of 2 equivalents of water.Indeed formic acid does not appear to affcct that particular degree of hydration so cha-racteristic of the acetic acid series. Hence it is also that we have no subformate of lead corresponding with the subacetate of lead and havc occasion to remark a general absence of basic formates. Thc physical properties of liquid formic acid are more suggestive of hydrocliloric acid than they are of acetic acid. The most concentrated formic acid that codti be prepared still contained 3.6 per cent. of water. The transpiration-time af that liquid it will be seen is 1.718 referred to water as 1 ; and of the %hydrate 1.486. There is evidence of retardation between tbe points of 3 and 4 equivalents of water but it is di&dt to say with which of these two hydrates the retardstion be con-nected.More numerous and minute obsetvations would Ire required to settle the point We can only draw the negative conclusion from the Table that the maximum retadation dm not coincide with the 2-hydrate aa in adc acid. 436 GRAHAM ON CAPILLARY LIQUID TRANSPIRATION TABLE V1.-Transpirati.on of Formic Acid at 20° by Capillary C shortened. (Transpiration-time of water 293 seconds.) Water added to 100 acid Water per Transpiration-time Spec. grat (CZHZO,). cent. In secofids. Water = 1. at 15'. 3 .73 8.6 603-5 1.718 1 *2265 19 $56.. 1 eq. 1G -35 484.5 1 *653 1.2019 39 -13.. 2 eqa. 20*93 435*Ei 1 -486 1.1765 ~ 68-69.. 3 eqs. 36.98 411 1.402 1.1524 68*47.. 3-5 eqs. 40 -64 401 -5 1.368 1 -1466 78.26..4 eqa 43*90 402.5 1 *372 1 1,1408 97 e82.. 5 eqs. 49.44 388-5 1.326 1.12'15 117.35.. 6 eqs. 53 -99 376*5 1*284 1.1203 136 -95.. 7 eqs. 67-79 359 1.226 1 *lo62 Hydrochloric Acid. The most concentrated form of this acid that was dealt with acid of sp. gr. 1.1553 contained already upwards of 8 equivalents of water. Its transpiration-time was 1.736 referred to the time of water as 1. With further dilution the time diminished till at the proportion of 12 equivalents of water the time had fallen to 1.5287. About this point the rate of diminutionis reduced and the transpiration-time even becomes stationary for a shoi t portion of the range of hydration. The retardation observed appears to coincide with the formation of a 12-hydrate of hydro-chloric acid.The existence of such a compound is further supported by the fact that solutions of hydrochloric acid tend to the same composition by evaporation at the atmospheric tempera- ture. The degree of hydration of most stability at high tern-peratnres and having the highest boiling-point is known to be st or near the proportion of the 16-hydrate. The existence however of the latter hydrate at the ordinary temperature is not supported by the transpiration experiments now recorded conducted as these were at a low temperature IN BELATION TO CHEMLCAL COMPOSITIO3J. 487 TABLE VI1.-Transpiration of Hydrochloric Acid at 20" by Capillary C. (Transpiration-timeof water 348 seconds.) Water added to 100 acid Water per Transpirationtime. Ilpec.grsv. ~~ ~ (HCI). cent. In seconds. Water = 1. at 15". ~- 221 '8 69 -23 604 1.7356 1 -1553 250 71 -42 669 1 -6336 1.1411 280 73 *67 636 1 -64G4 1*1303 290 295 -89 . . 12 eqa HO 300 74*36 74 .'14 76 *oo 532 632 620 1 -5287 1 -5287 1.4942 1-1246 310 7630 616 1 -4827 1-1201 380 79.20 486 1 -3966 1.lo21 394 310 .. 16 eqe.HC 79-97 80 -39 470 469 1 -3764 1-5416 1 -0992 1.0961 Akohol. The fundamental discovery m-ade by Poiseuille of a point of maximum retardation in the transpiration of diluted alcohol ia fully confirmed in the following aeries of obaervatious. The transpiration-time rises from that of absolute alcohol 1.1952 (water being l) to 2.7872 when the alcohol is united with 6 equivalent8 of water and then falls off again by further additions of water.TABLE VIIL-Transpiration of Alcohol at 20° by Capillary D. (Transpiration-timeof water 470 seconds.) Water added to 100 Water per Tranapiration-time. spec. grrv. 16'. I atAlcohol. cent. In seconds. 0 0 562 Water = 1. 1 -1957 1 3 6 7 10 20 33 0.99 2 -91 43'6 6 -54 9 -09 16 *66 23.07 578 615 650 695 734 861 950 1 *2297 1 3086 1 *3829 1 *4787 1.5617 1 *81C6 2 '0213 -7.469 *a030 -808% *8396 -8557 438 GRAHAM ON CAPILLARY LIQUID TRANSPIRATION TABLEVII1.-continued-Water added to 100 Water per Transpirationtime. Spec. grav. Alcohol. cent. In seconds. Water= 1. at 15". -_3 40 28.50 1029 2.1893 a8683 50 a3 '33 1083 2.3253 *8800 60 37.60 1152 2 -4510 *8897 70 41 -17 1213 2,5508 *a983 72.5 42 -02 1230 2 *6170 -9003 75 42 -85 1231 2 -6191 *g021 tla.26 ..4 eqs. HO 43.94 1239 2 -6361 *g045 80 44.44 1238 2 -6340 -9058 82.5 45 *20 1242 2 -6425 -9013 85 45 *94 1244 2.6468 *g088 90 47 -36 1256 2 -6723 -9120 lad 50 *OO 1268 2.6978 *9183 110 52 -38 1283 2 "1276 -9235 112.5 62 '94 1287 2 -7382 ,9249 115 63 *49 1298 2 *'is17 -9255 117.39,. 6 eqe. HO 54.04 1310 2 -7872 ,9271 120 64 -64 1307 2 -7808 *9288 122 55 *I25 1300 2,7659 a9292 125 55 a55 1297 2 -7595 *9304 130 56 *t2 1297 2,7595 *9328 140 68 -33 1295 2 -7553 *9363 150 60 .OO 1280 2 *7234 -9396 160 61 -53 1255 2 -6702 .9430 170 62 -92 1250 2 *6505 -9451 180 64 -28 1246 2 *6510 -9482 190 05 -61 1210 2 *6383 .Q500 66 *66 1235 2 *6276 ,9521 % 71 -42 1165 2.4757 -9601 800 75 -00 1094 -2 .a276 a9662 350 77 -77 1026 2.1829 89ti89 400 80 *OO 973 2.0702 -9716 450 81 -80 934' 1,9872 -9738 600 83.33 908 1*9s19 09769 It will be observed that after attaining its maximum the transpiration-time falls off in a very gradual manner till at least another equivalent of water has been added.With still further dilution the shortening of the transpiration-time is considerably more rapid. The Table appears to indicate a slight retardation at the proportion of four equivalents of water; but this would require confirmation. It is remarkable that hydrated liquid compounds appear in general to show only one decided transpira- tion maximum as with the l-hydrate in sulphuric acid the 2-hydrate in acetic acid the %hydrate in nitric acid the 6-hydrate in alcobol and the 12-hydrate in hydrochloric acid.IN RELATION TO CHEMICAL COMPOHITION. 1139 A considerable number of experiments were made upon speci-mens of methylic alcohol prepared at different times with some discrepancy in the resu\ts. Although always derived from crystallized methylic oxalic ether the liquid varied sensibly in transpirability. As the cause of this variation has not yet been ascertained I ahall confine myself at present to one statemcnt namely that a particular specimen of methylic alcohol gave 0 63 as the transpiration-time of the anhydrous subvtancc (water being l) and 1.8021 as the time of the 6-hydrate C,II,O + GHO and that for a considerable distance on either side of that point of hydration the transpiration was slightiy less and iicarly constant 3s it is in vinic alcohol.It may be inferred therefore with some probability that alcohols have n maximum of retardation at thc same stage of dilution. Three alcohols in a statc of' purity ivcre trampired through tlic same capillary with matcr for comparison at 20". The time of' water was $97 seconds. TABLE 1X.-Transpiration of Alcohols at 203. Transpiration-timc In seconds. Water = 1. Methylic alcohol . . . . 187 *25 0.630 -7973 66" C. Vinic alcohol . . . . . . . . . . 3.55 .1 1a195 A4mylic alcohol . . . . . . 1084 3.649 It will be remarked that the transpiration-time of an alcohol increases with the elevation of its temperature of ebullition.X similar observation applies to the transpiration of ethers. TAJJLE X.-Transpiration of' Ethers at 20" by Capillary C shortened. (Transpiratioii-time of watcr912%) seconds.) Transpiration-timc. In eeconds. I Water = 1 ---------i Formatc of.ctil)-i . . . . . . . 148 2 0-511 -9174 550.5 Acetate of etliyl . . . . . . . 160 *5 0*553 .S853 74 Hutyrate of' ethyi . . . . . 217 *5 0 *750 '*a490 114 Valerate of ethyl.. . . . *8760 133 *5 440 GUHAS ON OAPXUABY LIQUlD TBAXSPIBATION The tranepiration-times of the homologous acids previously obeerved appear also to follow in progression. Traiiapiration of Acids at 20'. Acid. Acid +2HO. Acetic acid ......l*2801 2-740 Butyric acid ...... 1.565 8.279 Valerinnic acid .... 2.155 8.889 The increase of the trtmspiratiou-time of an alcohol ether arid acid as each iises in its series may be connected with the in-creasing weight of their molecule. Acetone. The trawpiration of this liquid ia-remarkably rapid. It is ale0 greatly retarded by the addition of water. The time will be found to rise from 0.401 that of anhydrous acetone to 1604,the tinre of the 12-hydrate taking the equivalent of acetone aa C,H,O, or of thc 6-hydrate with the equivalent C,H,O. TABLE XI.-l'ranspiratiou of Acetoue at 20° by Capillary C. (Tranupiration-time of water 348seconds.) Water adtlcd to 100 Water Transpiration-time. Spec. grav. -~ acetone (C,B,,O,).at 16". per cent. In aeconde. Water =1. ~ ---v-7 --0 0 139-6 0 -401 -7943 15.61 .. 1 eq. 13 *42 212.5 0*610 -8384 31.03 .. 2 eqe. 23 *68 283.6 0.814 -8604 46.55 .. 3 , 31 *76 355.5 1-021 ,8850 62'06 .. 4 , 38 -29 457~ 10313 08990 77-58 .. 6 43 -68 464 1-333 -9128 J 85-34 .. 5.5 ,) 46 04 469 1.347 -9173 93.10 .. 6 , 48.21 482 1-385 19219 109 50 -00 500 1-436 *9251 108.61 .. 7 , 52 -06 515 '5 1-479 *9300 124.13 .. 8 ,) 55.33 531 *5 1-527 9320 139.65 .. 9 , 67-85 537.7 1-643 09413 155-lti .. 10 60 -81 552 -7 1-586 -9468 170.67 .. 11 ,) 63 -05 555 *5 1*594 *9604 186.18 .. 12 65 *05 558 *5 1-604 *9526 201 .71 .. 13 ,) 66 *85 556 -5 1-599 -9563 217-24 .. 14 , ti8 -41 557 1'600 '9588 232.75 .. 15 , 69 -94 553 *5 1*690 -9608 248.27 ..16 . 71 -28 549 1*677 *9632 263.79 .. 17 '72.23 547 1 5'11 -9649 279.31 .. 18 73.63 546 1-668 '9663 294.82 .. 10 ) 74 -67 539 -5 1-560 %676 372.21 .. 24 , 78 *82 519 1.491 -9736 I IN BELATION TO CEEYImL COypoBITIONe 441 The transpiration-time of acetone attains a maximum at what is rapresented in the Table as the compound with 12 equivalents of water. The time is nearly stationary for some digtauce on either side of that point tlic range from 10 to 15 equivalents of water being 1.586 to 1590 with 1*604as a maximum for the iutermcdiate twelfth equivalent. This liquid is too viscid in a state of purity to be transpired by i-neanu of' the bulb and capillaries employed in these experimentp. The observations to be recorded were confined to diluted solu- tiow of glycerin approaching in composition to the 18-hydrate C,H,06 t18HO.It was imagined that glycerin as a triatomic idcohol might affect combination with water in the proportion nimed. TABLEXI1.-Transpiration of Glycerin at 20° by Capillary C. (Transpiration-timeof water at the same temperature 34.8seconds.) Water added to 100 Ctly-ceriii (C6H306). Water per cent. Tranapiration-time. In secohde. Water= 1. ~~ ~ spec.grav. at 15". 1i0 62-96 1190 3.445 1 *lo10 176 -07.. 18 cqa.1 so 63 Ti 64-28 1160 1131 -5 3 -333 3.251 1 -0980 1 -0980 I90 65 -51 1068-6 3-070 1 -0984 192 65 T5 1054 3.081 1 -0927 195 197 66*LO 66*32 1049 1039 3 -014 2 977 1.0914 1 .oh2 200 66 -66 1028 2 4'48 1.0905 The transpiration-time of the 18-hydrate is 3.333 referred to water 8s 1.There is no iudication of a maximum at that point but the numbers descend according to their place in the Table without any interruption. The idea having suggested itself that the viamm property of glycerin-solutions might overpower or conceal the expected devia-tion the transpiration was repeated at a higher temperature when the solutioiis possess greater fluidity. 442 GRAHAM ON OAPILLARY LIQUID TRANSPIRATION TAHLE X1II.-Transpiration of Glycerin ?t Wo,by Capillary C. (Traiispir:Ltion-timeof water at the same temperature 186 scconds.) Watcr added to 100Uly-cerin (C,H,O,). Water per ccnt. Tmnspiration-timc. In seconds. I Water = 1. Spec. gmv. at 15'. lio 62 *96 435-5 2.311 1.1010 175 '5 68*30 432 2 922 1 *OD99 175 63*63 428 2*301 1 *0980 176 *08 .18 eye.177 63*77 63 *96 425 422 '5 2*a84 2 -271 1.0976 1*0970 180 64.22 420 2.268 1 '0960 Still no retardation appears at the point of 18 equivalents but the time continues to shorten as the proportion of water is increased according to a pretty uniform progression. The in-formation respecting the constitution of glycerin which transpirn- tion affords is therefore of a negative character. The existence of a relation between the trmspirability of liquids and their chemical composition appears to be established. It is a relation analogous in character to that aubsisting between the boiling-point and composition so-well defined by Her mann Kopp. Perhaps the most interesting part of the present subject to develop would be the transpiration of homologous series of sub-stances.Judging from the limited observations on the alcohols ethers and acids tlic order of succession of individual substances in aiiy series would be indicated by the degree of transpirability of these substances as clearly as it is by their comparative volatility In carrying out the inquiry it would probably be found ad-vantageous to operate at a fixed and somewhat elevated tempera- ture. A large number of substanccs arc liquid at looo of which the transpiration-time could be easily o1,tainecI. In hydrated substanccs transpiration also affords a manifestation of definite combination at oncc striking and precise. I need only refer to tlie manner in which tlie ''constitutional" hydrate of sulphuric acid SHO +HO of acetic acid C41-1404+3H0 of nitric acid NH06+3H0 aiid of alcohol C IT 0 +6HO is cacb indicated by its maximum transpiration-ti&.&e indication of the alcohol-hydrate is particularly distinct althougli that hydrate IN RELATION TO CHEMICAL COMPOSITION. 443 must be a comparatively feeble compound. Indeed the extent to which transpiration is affected by the annexation of constitutional water appears to be by no means in proportion to the intensity of combination. The increased resistance to transpiration observed in thesc definite hydrates may be connected with their larger molecules. But another speculative view of the retardation can be suggested in which the phenomenon is referred to a physical agency.When one of these definite hydrates say the 6-hydrate of alcohol is being forced through the capillary it may be imagined that a small portion of the hydrated compound is molecularily decom- posed by the friction. A certain portion of the impelling force wodd thereby be lost being converted into the latent heat which alcobol and water require to amme when separated from each other and the transpiration be consequently retdrded; for as alcohol and water evolve heat on combining so they must absorb heat when their union is dissolved by any cause. But the cbange of temperature representing the lost force appears to be too small to be rendered sensible to observation. It would be capahle of raising the temperature of the transpired liquid not more than about one forty-third pat of a degree according io an accurate estimate for which I am indebted to Professor Stokes.In con-sequence of this circumstance the physical hypothesis now suggested has neither been verified nor disproved. To this paper are appended two series of observations made on transpiration at different temperatures the first series being the transpiration of water and the second that of absolute alcohol. Each series of experiments is repeated with two capillary tubes one having nearly double the resistance of the other. The numbers from the two capillaries exhibit a fair amount of agree-ment. The times given are those actually observed no correction being made for the small variation of the capillary in diameter at different temperatures.The dimensions of Capillary D were as follows :-Capacity of bulb 4.135 cub. cent.; length of capillary tube 37.5 millims.; diameter of bore 0.10325 millim. Time of passage of water at 20° under pressure of one atmosphere 470 seconds. The dimensions of Capillary E were as follows :-Capacity of bulb 3.725 cub. cent. ;length of capillary 53 millims. ;diameter of bore 0.0858 millim. Time of passage of water at ZOO under pressure of one atmosphere 913 seconds. TABLEXV.-Transpiration of Alcohol at different Temperatures. By capillary tube D. By capillary tube E. .-Time and velocity of water Time and velocity of water .s! 4 Time and velocity of water Time and velocity of water 11 3 24 at 20°=1.8t 0"-1. at 20" = 1. at 0" = 1. gm ocl 3 s& Time. Velocjty. Time. Velocity. Time. Velocity. Time. Velocity. -2 -----0 oc. 860 1.8297 0 -5466 1.0238 0 *9767 1642 1-7984 0.5560 1-0079 0 *9920 1 840 1-7893 0 -5688 190012 0 -9988 1601 1-7635 0 -5702 0 -9828 1.0174 3 607 1.7170 0 -5824 0 -9607 1a0409 1537 1-6834 0 '5940 0 -9435 1-0 59.8 3 772 1.6425 0 -6089 0 -M90 1'0880 1473 1-6164 0 -6198 0 -9042 1-1059 7 733 1-6902 0 08368 0 -8785 1-1382 1410 1-5443 0 -6475 0 -8656 1-1553 10 700 1-4893 0,6714 0 -8333 1-2000 1350 1-4786 0 '6755 0 -8226 1-2066 15 624 1-3276 0 *7532 0.7428 1 -3461 1213 19285 0 T526 0 -7446 1*3429 20 562 1-1957 0 -8362 0 $690 1-4946 1092 1.1960 0 '8360 0 -6703 1.4917 25 520 1-1063 0 -9038 0 *6190 1-6154 1001 1'0963 0 -91 20 0-6145 1.6273 30 476 1-0127 0 -9873 0 -5566 1.7646 916 1'0022 0,9978 0 *5617 1*7803 36 428 0 *9106 1-0981 0 -5095 1-9626 843 0 -9253 1'0830 0 -5175 1'9323 40 391 0 -8319 1*2020 0 -4654 2 -1483 772 0 '8465 1.1826 0 -4739 2 -1101 45 360 0 *7659 1-3055 0 -4285 2 *3333 707 0 '7743 1*2913 0 4340 2 *3041 50 331.0 TO63 1-4157 0 S946 2 -6339 646 0 '7064 1*4155 0 * 3959 2 *5100 65 307 0.6631 1*5309 0 03664 2 -7301 592 0.6484 1-5422 0 -3634 2 *7517 60 285 0 *6068 1 -6491 0 -3392 2'*9373 561 0 '6085 1*6569 0 -3382 2 -9564 65 262 0 -6674 I *8006 0 3119 3 *2061 610 0 -6685 1*7901 0 -3130 3-1941 70 241 0 -6127 1-9602 0 -2869 a 468 0 -6125 1-9466 0 *2873 3 *4807 TABLEX1V.-Transpiration of Water at different Temperatures. By capillary tube D.By capillary tube E. -Pime and velocity of water Time and velocity of water Time and velocity of water Timeand velocity of water B at 20" = 1. at 0" = 1. 24 at 20" = 1. at 0"= 1. B a !i! i$ Time. Velocity. 1 r3 .-Time. Velocity. g% Time. Velocity. Time. Velocity. 840 1 *7872 1-1. 1629 1 *7872 0 -5604 1' 1. 1 792 1 '6851 0*5934 0* 9428 1 *0606 1568 1 '7174 0.5839 0.9626 1 -0389 2 770.5 1 *6391 0-6099 0*9l72 1-1514 1 -6582 0*do50 0 *9294 1-3 749 1 *5936 0.%235 0*8917 1 *1216 1461 1 *6002 0-6249 0*a976 1 *1449 4 727 1 *5468 0.6465 0-8654 1- 6 709 1*5085 0-6629 093440 1 -1857 1382 1.5136 0*6606 0 -8483 1.1787 7 669 1-4234 0-7025. 0-7964 1 -2556 1289 1.4118 0*7083 0.7912 1 -2ii38 10 618 1-3148 0-7606 0-7357 1 *3592 1188 1-3012 09385 0.7293 1 *3717 14 548 1 -1659 0.8576 0-6423 1 '5328 16 533 1 -1340 0-8818 0.6345 1 -5759 1037 1 *1358 0 *886)4 0*6366 1 +5709 16 521 1.1086 0-9021 0.6202 1.6122 20 470 1-1-0-6695 1 '7872 91 3 1' 1.0*ti604 1 *7842 25 414 0*8808 1 -1362 0-4928 2*0189 823 0-9014 1 *0904 0-5052 1 -9793 30 375'5 0-7989 1.2616 0-4470 2 *2371 743 0-8138 1 -2288 0-4501 2.1924 36 338 0-7191 1,3905 0-4023 2 -4852 6'70 09338 1 9626 0.4113 2 -4313 40 309'5 0-6608 1.5185 I 0-3684 2-7108 602 04593 1 -6166 0-3695 2-7059 46 284'6 0-6053 1 -6520 0-3386 2-9526 558 0*6056 1.6609 0*3394 2-9459 60 261 0-6553 1 -8007 0-3107 3 -2184 505 0.5531 1 -8079 0-3100 3 -2257 66 243 0*5170 1 -9341 0-2892 3.4979 475 0-6202 1.9221 0-2916 3 -4294 GO 228 004851 2 aOti1'4 0 &I4 3 -6842 438 0-4797 2-0844 0-2689 3 9191 66 214 0*4653 2 -1967 0.2547 3 -9252 400 0*4381 2 -2826 0-2455 4-0726 70 200 0-4155 2 -3500 0-2380 4 -2000 378 0.4140 2 -4163 0*2321 4 3122 -

ISSN:0368-1769    

DOI:10.1039/JS8621500427

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

44G ANDERSON ON THE CHENISTRT OF OPLUAL. [A Discourse delivered to the Fellows of the Chcmictll Sooicty May lst 1862.1 By THOMAS M.D. F.R.S.E. Professor of Chemistry ANDERSON in the University of Glirsgow. THEchemical history of opinm may be said-to have its origin so far back as the year 1803 when Desrone announced that he htd extracted from it a peculiar crystalline substance in which lie helieved its narcotic properties to reside. In a chemical point of view his investigation was of minor importance and it would scarcely merit notice if it mcre not tliat it had an important influence in starting the idea mliich has proved so prolific in im- portant results that the therapeutic properties of iiiediciiial sub-stances depend upon the preseiioe of particnlar active principles readily separable from the inert rnattcrs of ivliich their bulk is composed.D esroae evaporated tlic nqucous solution of osium to a syrup and after allowing it to stand fur soiiie time a gritty matter deposited which was scarcely soluble in wntcr but crystnl- lised easily from alcoliol aiid ether. From liis description of its properties it was obviously nsrcotine ; but hc did not observe its power of combining with acids and his observatioiiu wcrc far ii.oin definite and ditl not attract much attention. No one intlccd appears to Iiave followcrl thn up until the year 1817 when $3er turner made th nest step in tlic investi- gation of opium and published tlic result of researclics which had occupied him for several years. Hc detectcd incconic acid and morphia but curiously enough failed to obtsiii D esronc’s sub-stp.nce which he thereforc supposed to haw bccii a.niecoiiate of ... morphia. A considerable time agaiii elapsed witliout aiiy further pro-gress being made ;but in 2826 D ulilnnc discovered mecoiiine and described its propertics wry distinctly although he did not give it a name-an oniissioii supplied by Couei-bc in 1830. During tlie several years followiiig the latter datc opium was sill)-jected to a very iniiiute investi@ioii by Couerhe Pellc tier Robiquet Mer ck and others who added codeine thebaiiie narceine and porphproxine to the list of its crystalline constituents. Subsequently to their time little mas done except to add a few 447 ANDERSON ON THE CHEXMISTKY OF OPIUX.analyses of tlie substances discovered by these observers but with- out extending in any marked degree our knowledge of their chemical relations until 1844 when TITohl er and B1y th separately examined narcotine and made it tlie starting point of a very remarkable series of products. In the year 1850 I was myself induced to commence the study of some of the principles of opium ; and at that time I found our knowledge sufficiently extensive but greatly deficient in pre-cision. The constitution of meconic acid morphia and narcotine appeared sufficiently established ;thpt of codeine was expressed by several different formulae of which one recently proposed by Gerhardt had probability in its favour and mas fully confirmed by my own researches; but all that was known regarding the other subtances was in the last degree unsatisfactory and based on the imperfect and often conflicting statements of their dis- coverers and on analyses made at a time when the methods in use were deficient in that accuracy and precision which they have since attained.It was obvious indeed that the whole subject required revision and I made it my task to do this in the first instance; but I was naturally led to extend my investigation to the study of the prodccts of decomposition of the different sub. stances so far as the amount of material at my disposal permitted and I am still engaged with the subject. The mass of facts which has now been accumulated regarding the chemistry of opium renders it necessary for me to discuss it very succinctly here and without entering into details.I pass altogether without mention its indeterminate constituents although many curious observations have been made in relation to them and proceed at once to the crystalline substances of which no fewer than twelve-nine well-determined and three doubtful-have been described. They are- Morphiue. Thebaine. Porph yroxine ? Codeine. Narceine. Opianine ? Papaverine. Meconiiie. Mcconic acid. Narcotine. Pseudomorphine ? Thebolactic acid. A critical review of the processes employed for the preparation of these substances would be of much interest though by no means suited to the present occasion. It is very obvious that the results ohtained by different experimenters have greatly depended on the methods they have pursued.We observe that one individual obtains 428 ANDERSON ON TEE CHEMISTRY OF OPIUM. particular srhstauces abundantly mother only in very small qiaan-tits aud the difference is often due to modifications in the mode of working which at first sight appear very trihg. Even the quantity of water employed in the primary solution of the opium is important and greatly affects the quantity of resino'id mattera dissolved and by consequence the facility with which some of the bases are made to separate in the crystalline form. Thus I have found narceine very abundantly while other observers obtain it in small quantity and have altogether failed to detect pseudo- morphine and porphyroxine although I have sought for them with some care ;nor lirtve I noticed thebolactic acid which the Mesera.Smith state they separate in large quantity. It is true that my attention has not been directed to the acids of opium ;but had the substance in question been easily obtainable in the course of the process I have followed it could scarcely have been overlooked. Tlie investigator of opium is placed at a certain disadvantage by the necessity of making use of the refuse of the manufacture of morphine by processes in y7liicl1 everything is sacrificed to obtain- iiig the maximum quantity of that alkaloid irrespective of the others associated with it and for the preparationof which it by no meitiis follows that they are equally advantageous and it can scaxcely bc doubted that if it were possible to operate on a hundred weight or two of opium by methods entirely different from those iiow in use results of much interest might bc obtained.For the preparation ofinorphiue the process originally proposed by Robertson and Grcgory has iu tliis country at 1eaatJproved itself the most suitable and in skilful hands is found to yield a larger proportion of the base than any other. It is so well known that it is hardly necessary to refer to it here the more especially as so far as I know;no chaiige has taken place in the principle on which it is founded although of course there is abundaiit seope for judgment and skill in carrying out the manipulativc details. The principle involved is very simple.The bases are present in opium chiefly as meconates which are difficultly crystallisable salts ; but on the addition of chloride of calcium meconate of lime precipitates and the chlorides remain in the solution of which the hydrochlorates of morphine asd codeine are readily crystallisable and separate from the concentrated solution leaving the other bases behind in the mother-liquor. It is from the residue left after ANDERSON ON THE OHEMTSTRY OF OPIUM. 449 complete separation of the morphine that I have extracted the bases I examined and the process 1 have found most convenient is the following :-The mother-liquor which has the consistence of treacle and is perfectly black is diluted with water and animoiiia added. An abundant dark-brown precipitate falls corisisting of narcotine papawrine and thebaine accompanied as I have recently observed by a sinall quantity of cc;deine the presence of which could scarcely have been expected and all contaminated with a brown resinous substance.This precipitate which is at first quite granular runs togetlier into a resinous mass if allowed to lie in the fluid and the mother-liquor is thus squeezed out of it as effectually as if it were put into a powerful press. By solution of this pre- cipitate in boiling spirit impure crystals of narcotine are obtained on cooling which may be purified by animal charcoal and succes- sive crystallisstions. By distilling down the solution a further crop of crystals is dissolved and finally a dark mother-liquor is obtained from which thebbine arid papaverine may be prepared.For this purpose water is added ; the liquid is rendered slightly acid by acetic acid; and the resin which is thus separated is filtered off; subacetzte of lead is then added to the filtrate until it restores the blue of reddened litmus ; and the precipitate being Separated the excess of lead is removed by sulphuretted hydrogen or more conveniently by sulphuric acid. Ammonia then precipitates the thehaine still contaminated witli resinous matters from which it is separated by crystallisation from absolute alcohol and decolo- rised by animal charcoal. Papaverine may be extracted from the Icad-precipitate by digesting it with alcohol evaporating the liquid treating it with hydrochloric acid filtering frorn resin concentra- ting and leaving the solution to itself for some time when the sparingly solrible hydrochlorate of papaverine slowly crystallises.Yrecipitation with ammonia and crystallisation from spirit give the base itself in a state of purity. The mother-liquor from which the precipitate of these bases has been separated contains narceine and meconine with a small quantity of papaverine. On concentrating it narceine separates in abundance and is easily obtained pure by washing with a small quantity of cold water and crystallisating two or three times. It is remarkably distinguished by the facility with which it is obtained free of colour for which purpose animal charcoal is not required. 450 ANDERSON ON TFIE CHRMIS'l'RY OF OPIUM.After concentrating the liquid until the narceine is separated the residue is agitated with ether which estraets meconine together with a little papavcr'iiie. Meconic acid is prepared from the meconate of lime obtained in the first part of Robert son and Gregory's process according to a. method well-linown. Of the preparation of thebolactic acid no description has Jet been published. Jfoiphine by far the most important of the constituents of opium is as yet but imperfectly examined. Its constitution long expressed in chemical works by the formula C35H20N05 ; this formula was altered by Gerhardt to C,,II1,NO6 which has been universally adopted arid confirmed by subsequent researches. Little is known regarding the products of its decomposition; but the researches of How hare shown that it belongs like most of the other natural alkaloids to the group of nitril bases.It exists in opium to the extent of about 10 or 12 per cent. but the proportion differs greatly in different varieties being largest in opium produced from the poppy grown iti thir country which is said to have yielded as much as 20 per cent. while in East India and in Egyptian opitim it often does not exceed 5 or 6 per cent. Turkey opium is that from which it is most commonly extracted but even then its quality varies very greatly ; and as the amount contained in different specimens is a matter of much importance to themanufacturer various atiempts havc been made to devise a method by which the amount contained in a given sample might be quickly and accurately ascertained.M oh r and other chemists have given processes for this purpose; bnt none of them have proved trustworthy the fact being that the conditions under which niorphine is completely separated differ for every sample and the manufacturer finds it much safer to rely upon his eye which enables an experienced observer to form an opinion which if not always correct is safer than any chetnical process. The introcluction of Robertson ahd Gregory's process led to the discovery of codeine Robiquet having observed that when the morphine was precipitated from the muriate obtained by it another base remained in solution along with the sal-ammoniac formed. His idea was that the liquid contained a double salt of codeine and ammonia.But I have satisfied myself that this view is erroneous having obtained pure hydrochlorate of codeine from the liquid by crystallisation alone. The earlier analyses of codeine led to the conclusion that it ANDEKBON ON THE CI1EMIBTKY OF OPIUX. 45 1 differed from morphine by a single cquivalcnt of oxygen arid it was reprcscutcd hy the formula C:,,H,,KO,, vliich was called it1 question hy Gcrhardt. Ilc made two atialyses of the Iiydratctl haw atid obtaiticd rcdts corresponding with C3$12p06 which I have fully confirmctl. Cotleirie therefore so far as it* constitution is concerrietl may hc consitleretl as a homologue of morphine but they prcscrit iiottc of that similarity iu pro-pertics which is usually so conJpicuous in the adjacent rnctnl,crs of' a hotnologous scries.Nothitig intlcctl can he inow Indied than the difference hetween morphine insoluble iil witcr ant1 cthcr and but sparingly dissolved by alcohol tirid co:lcinc wtiicli is readily and abuntlantly taken up hy all these mcIiztru3. Othcr differences rtlso esist which rcnder it very qucstionahie wlictlicr the two bases can be coilsidered as hornohgous. C'ocleirie yir~lrls many beautiful sul,stitution-proclucts which are ohtainccl witli some difficulty. I have described nitro-codeine C,GII,,(SL),)SO, clilorocodeine C36H,,ClN06 and bromocodeinc C3611201jrS06 all obtained by the cautious action of the different suhstaticcs on the base itself and remarkably definite compoiincls. Indications of an iodine substitution-compound were ds~ obtained ;hut tlic most remarkable iodine-compound is that which I have called tcriodoco- deine without intending thereby to define its cliemica! nature.It contains ttre elements of one equivalent of (odcitie and tliree equivalents of iodine and belongs to a class of compouitds of whose rational constitution we have no tlefiriite ideas. It is ob-tairied in beautiful doubly oblique crystals displaying the pllzno-mena of pleochroism in a very striking manner. 7'hebuine was discovered by Pellc tier in 18312 mil clcscribed by him urider the name of paramorphine his analysis hii\iiig led to the conclusion that it was isomeric with morphine; thc inac- curacy of this opinionwas shown by Couerbe and Kanc altliough neither of them succeeded in fixing its true constitution.Rfy own analyses show that it contains C38€121N06,thus differing from codeine by two eqqivalents of carbon. It is quite iiisoluble in water but extremely soluble in alcohol and ether from the former of which it is deposited in tabular crystals on cooling. Strong sulphuric acid produces with it a dzep red colour. When diluted the acid dissolves it and on standiug for some time a resinous substance deposits vhich on treatment with boiling water dissolves and on cooling gives sparingly soluble crjstals. Its salts crystallise well. Of its decomposition-products nothing ANDERSON ON THE CHEYIBTRY 01 OPIUM. is yet known but as I have now obtained a larger quantity of the base I trust I may at no distant date be enabled to supply some information 011 this point.Papavereine.-This hsc was discovered by G. Merck in 1850 and was obtained from an old opium rcsidiie. It appears how-ever to be ail invnrinldc constitucnt of opinni and in riot incon- siderahle qiiantity. It is obtaincd in sinall nccdles generally groupcd in radiated masses highly soluble in boiling alcohol and dktinguishcd from the other opium-bases by giving a fine blue with concentrated sulphuric acid. Its salts crystallise well the hydrochlorate more particularly being obtained in fine crystals. Its formula is C4,T12,K0,. One of its most singular peculiarities is its tendency to carry down with it ammonia when precipitated by that base ; both Merck and myself obtained in its analysis a quantity of nitrogen considcrably in excess of the theoretical quantity and it was only by precipitating with potash that 1 succeeded in obtaining an accurate result.It yields several well- marked substitution products among which nitropapaverine which crystallises in pale buff needles and yields sparingly soluble salts and bromopapavcrine are the most characteristic. Narceine is distinguished from all the other opium-bases by its solubility in watcr whence it crystallises in fine silky needles which are deposited in such ahundance that a solution saturated at the boiling point becomes nearly solid on cooling. Its basic properties arc very feeble so much so indeed that both Pelletier its discoverer and C ouerbe who afterwards examined it main- tain that it is incapable of combining with acids; but in this respect they were in error for it gives well-marked salts.Its formula is C46W29N018.Its decompositions are as yet un-known but I have obscrveil that it is capable of producing certain substitution-products and also of undergoing further changes which I intend to investigate further. Narcotine is hy far the most interesting and remarkable of the opium-bases. Indeed its remarkable decorn positions and the number of highly crystalline products it yields give it claims to be considered as the most interesting of the natural alkaloids. Although discovercd by Desrone at the beginning of the preseiit century its chemical history may he said to date from the year 1834,when Wiihler and Blyth separately obtained some of its most important decomposition-products.TiT6hl er found that when treated with oxide of manganese and sulphuric acid it vielded a new base and acid which he called cotarnine and ANDEItBON ON TIlE CMEMISTRY OF OPIUM. 453 opiardc acid. Blyth in endeavouririg to determine the con-stitution of narcotine by the aialysis of its platinum-salt observed that an excess of bichloride of platinuni produced the same de- composition. His investigation led Iiiin to the conclusion that its formula was C46t125N014 which afforded a sufficient explanation of the results obtained by Wiihler and himself and also har-monized with the researches I made at a subsequent period. More recently Messrs.Matthiessen and Foster have again revised the formula of narcotine arid give C,HmNO, as the neareat expression of their results and as likewise affording an easy explanation of its products of decomposition. It ia not possible in the present state of our knowledge to decide positively between these two formulze and a similar uncertainty exists as to that of cotaruine for which Rlyth's analyses give C26H13N06,and those of Matthiemen and Foster C,H,,NO,; but there is no doubt as to the constitution of the non-nitrogenous substances produced along with it. Wohler and Blyth obtained only opianic and hemipinic acids by treating narcotine; but by using nitric acid I obtained in addition another substance which proved to be meconine a base long before obtained by Couerbe existing ready formed in opium and having the formula C,,H,,O,.Opianic and hemipinic acids which me simultaneously produced may be considered a? higher degrees of oxidatiou of this substance being respectively C20H10010 and C2,HIoO1,. The explanation of the decomposition of narcotine by oxidising agents must differ according as we accept the formule of Blyth or those of Matthiessen and Foster. Aicording to the former narcotine may be represented as if it were a compound of meconine and cotarnine plus hydrogen. Thus-and the action consists in the oxidation of two equivalents of hydrogen while the further addition of two or four equivalents of oxygen would produce opiariic or hemipinic acid. According to the latter view narcotine would be simply a compound of meconine and cotarnine thus- and in that case the formation of opianic and hemipinic acids would be due to the direct addition of 0 or 0, while the breaking up into meconine and cotarnine must be explained upon 454 ANl>EICSC)N ON THE CIIEMISTlZY OF OPIUM.a different principle. An experiment madc by me long since and to which refererice is made at the close of one of my papers,* may serve to throw some light on this point. I exposcd narcotine along with a slight excess of sulphirric acid to a heat of 280"F. in a sealed tube and thus obtairwtl sulpliate of cotarriine and mccmine and we may suppose that wlicn thc lattcr srrbstance is obtaincd by the action of nitric acid thc clmrigc in both caws may be clue to the strong acid simply expelling the mecoriinc from its combina- tion with cotnrniric.It is fair to say however that the action is not so simplc 8s licre represented and I invariably found that a dark-colourcd substmcc was produced at the same time the propertics of which I havc riot yet cxamined. Meconiiic or opianyl as I prefer to call it opianic and hemipinic acids as well as cotarriitie are capable of yielding an extensive scrics of products of the moat interesting kind the relations of which arc howcver far from being as yet completely worked out and tlic discussion of whose properties would carry us far beyorid the limits of the present paper. It is impossible however to avoid mciitioniiig the facility with which they all yield methyl- compounds.Thus narcotinc when treated with hydriodic acid gives 3 cqnivalctits of iodide of methyl and cotarnine and its products give methylamine with great ease. This is particularly tlic case with apophyllic acid which when boiled with excess of potash evolvcs it readily and an acid free from nitrogen is obtained. Apophyllic acid which is formed by the action of nitrio acid 011 cotamine is C16H,NOS and my observations lead me to S1lJ)pOSC that it is c2 methylamic acid ; should further investiga- tions establish tliis it would be represcnted by the formula C,4H2(C,II,N)0, and contain an acid CI4H4Ol0,which must bear a near relation to rriecoiiic acid thus- ................ C,4H4010 Supposed new acid Meconic acid.. ...................C,,H40, Some years since Wertheim announced that he had as-certained the existence of three difl'erent kinds of narcotine in opium which he called methylo- ethylo- and propylo-narcotine. These substances however I have been unable to detect although a considerable number of different specimens of narcotine have passed through my hands ; and as Messrs. Matthiessen and * Edinburgh Philosophical Traneactions vol. xxi. part i ANDERSON ON TnE CHEMISTRY OF OPIUM. Foster have come to the same conclusion little doubt can be entertained that Wertheim’s idea is erroneoils. It will scarcely be necessary for me to refer at length to the three doubtful constituents of opium except to say that they require further investigation. I must observe however that although I have followed as nearly as Circumstances would permit the process given for their preparation I have failed to detect the slightest indication of them; and it is probable that they are met with only in particular kinds of opium and in exceptional circumstances.This is certainly the case with opianine which Hinterberger states he found in Egyptian opium and in regard to which his statements are very imperfect. He originally gave for it the formula C66H36NO23 which he afterwards altered to C66H36N2021 but in neither case is there any satisfactory evidence of the accuracy of the results. Still less can be said for the formula C,,H 8N024assigned to pseudomorphine and as to por- phyroxine nothing is known. It has often been a matter of discussion whether these sub- stances which have been obtained from opium are to be con-sidered as educts or as products that is whether they pre-exist in it or are the result of deconipositions occurring during the process of extraction.As a chemical question it would of course be most interesting to ascertain that they were products. The dis- covery of the decomposition of narcotine with the production of meconine may be taken as pretty conclusive evidence that it at least is a product ; and if so it may be fairly inferred that cotarnine must exist in the opium although it has not been detected therein. Thcse however who are best acquainted with the properties of that base will best understand the difficulty which besets its separation from such a substance a opium and will not be inclined to doubt that it must exist there.As regards all the other constituents of opium they must be considered as educte for notwithstanding a tolerably close con- nection between the formule of some of them there is no evidence as to any relationship in constitution. We speak however on this point in ignorance ; for what has now been said is sufficient to show that notwithstanding the mass of facts accumulated our knowledge of many of the opium constituents is far from perfect and that there is abundant scope for further investigation.

ISSN:0368-1769    

DOI:10.1039/JS8621500446

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

456 ERLENMEYER AND WANELYN ON Lll1.-On the Constitution of Melampyrin. and J. A. WANELPN, By Dr. ERLENMEYER ESQ. IN our paper on BIannite* we remarked that notwitlistanding the abundance of that substance and the labour which had been bestowed upon its investigation chemists were by no means sure of its formula. We showed further that by subjecting that body to the action of hydriodic acid iodide of hexyl was formed; and thus w+e estahlished the formula which is in general-use. But if-a degree of doubt existed as to the real composition of mannite what sliall we say about the composition of the rare members of the mannite family some of which obtained in small quantities from rare plants have been investigated only by their di scov er em. In a recent paper bearing the title “On the identity of Melam- pyrin with Dulcit,”? Gilmer has pointed out very strikingly one of the peculiar difficulties which beset the investigation of this class of compounds.Gilmer analysed melampyrin and then found that there were three probable formulae which expressed his analysis:-CiH.205 CbHIQOB CIH1607 * A * C .... 39-47 .... 39.56 .... 39*62 H .... 7-90 .... 7.70 .... 7-55 0 .... 52*63 .... 52.74 .... 52-83 100.00 100~00 100*00 To distinguish between these three bodies Gilm er prepared a crystalline baryta-derivative. Between C6H12B%06and either C5H,,Ba,0 or C,Hl,Ba20 there is a difference of from 1.5 to 2 in the percentage of carbon so that an analysis is capable of de- termining the difference.Gilmer has fixed upon the formula C6H,,Ba,06 and consequently he writes CGH,,~~ for melampyrin. We have been for some time back investigating the action of hydriodic acid upon different members of the sugar and mannite group. On the present occasion we publish our experiments on Proceedings of the Royal Bociety of Edinburgh 1861-62. t Ann. Ch. Pharm. crxiii 8’12. TIIE CONSTITUTION OF MELAMPYRIX. melampyrin. As will be evident by-and-bye we likewise fix upon thc formula C6H1406,but we think it will be conceded that the nietliod which we are adopting is calculated to furnish results of higher certainty than that followed by Gilmer. Here are three iodides corresponding to tlie three probable formuk for melam- yyrin :- C CiHllI ....30-30 .... CbH13I 33.96 .... CIHd 37-17 H .... 5.56 .... 6-13 .... 6-64 r .... 6~4.... 59-91 .... 56-19- 100*00 100~00 100*00 The carbon-difference is as will be observed between 3 and 4 per cent. Furthermore there is a wide difference between the boiling points of these iodides; and from each one derivatives may be got which present all manner of physical differences. But there is another particular to which we would direct atten- tion. Gilmer’s baryta-derivative can at the utmost only establish that the molecular weight of melampyriii requires the formula C6H,,06. It leaves quite unanswered the question is the carbon group C contained in the compound? Still the question might becproposed has melampyrin the nature of an ether? It leaves unnegatived these formulae for instance :-......*.*... By operating with hydriodic acid this question is at once set at rest. The obtaining of iodide of hexyl from melampyrin not only settles the molecular weight of that substance but ale0 shows that the carbon-condensation is 6. Among the rather numerous members of the mannite family we shall perhaps find some examples of the ether-€mula just given. The details of our experimeuts upon melampyrin are these The melampyrin which we used was obtained from E.Merk of Darmstadt from whom we have ascertained the following particu-lars relative to its preparation. It was obtained bm Melampynrm imnorosurn and .M. vtllgalocm. ERLENMEYER AND WANICLYN ON Obviously it was of importance to test whether it was free from mannite.For this purpose we availed ourselvcs of the striking difference between the solubility of the two bodies in cold water. The solubility of mannite at 16O C. is 16 in 100 parts of water. The solubility of rnelampyrin on the other hand at the same temperature is according to Gilmer,* 8.4 in 100 parts of watcr. We made a determination of the solubility of our melampyrin in water arid also under precisely similar circumstances a deter- mination of the solubility of mannite. Inasmuch as we took care to keep the solution of melampyrin for several hours in contact with a large excess of finely powdered melampyrin it is obvious that if our melampyrin liad contained any considerable proportion of mannite we should have got a number nearly approaching to the solubility of mannite.Nothing of the kind was observed for these are our results :-I. 100 parts of water at 16*5OC. dissolved 2.94 parts of melampyrin. 11. 100 parts of water at 16.5OC. dissolved 16.07 parts of m annit e. Our melampyrin was therefore free from mannite. It was analysed with the following results. *3353grm. of the substance burnt with chromate of lead and a little bichromate of potash gave ,2384grm. of water and *4835grm. of carbonic acid. Calculated. Found. C .... 7-72 .. 39.56 ........ 39.33 Hi4 .... 14 .. 7.70 ........ 7.90 0 .... 96 .. 52.74 182 lOO.00 In one operation 4 grm. of melampyrin were heated in a stream of carbonic acid with 60 cub. cent. of strong hydriodic acid (boiling at 124’C).The dark-coloured oily distillate was distilled in contact with water after having been freed from excess of iodine by means of sulphite of soda. The colourless oil which distilled weighed 2 grm. On a larger scale the reaction did not seem to be ao neat for in * Ann. Ch. Pharm. cxxiii 37’1. In Gilmer’s paper there ie a press.emr 34 instead of 3.4 with which latter number Gilmer’s experiment agrees. TEE CONSTITUTION OF MELAMPYRIN. a second operation 20 grms. of melampyrin gave only 5.5 cub. cent. of crude iodide. The amount of hydriodic acid (boiling at 126OC.) which was used in this experiment was 230 cub. cent. The crude iodide which distilled over was mashed with sulphite of soda and then redistilled in contact with water and in a stream of carbonic acid.After being dried with fused chloride of calcium it could be distilled alone without much decomposition taking place. It was slightly coloured and boiled at 165" to 175OC. (We have previously found that iodide of hexyl boils between these points.) Analyses of our product gave these results :-I. -2317grm. burnt with chromate of lead copper-turnings being used gave 01320grm. water and -2936 grm. car-bonic acid. 11. -2338grm. gave 01360grm. water and *2982 grrn. CO,. 111. *57Wgrm. were sealed up with ethylate of sodium and heated in the water-bath for several hours. The iodide of sodium so formed was precipitated with nitrate of silver. The iodide of silver obtained weighed *6285grm. Calculated.Found. r- I. 11. 111. C H, I 72 13 k27 33.96 6.13 59-91 34.56 6-33 .. 3478 6-46 .. 58-66 c_ CI- 212 100*00 Hence it will be seen that the liquid was iodide of hexyl the difference between the percentage of carbon required by iodide of hexyl and that required by iodide of heptyl being more than 3. In order to confirm our result me digested some of the liquid with alcoholic solution of potash for several hours; we then dis- tilled in the water,batb and added water to the distillate. An oil lighter than water and having the smell of hexylene sepa- rated. This oil was dried with chloride of calcium and then distilled. It boiled art 68" to 70"C.(the boiling point of hexylene); the retort was dry below 90°C. It was next saturated with bro-mine with which it combined with great violence.The result- ing bibromide W~B analysed. 1. *2803pi. burnt with cliromate of lead and a little bichro- mate of potash gave *29-58 grm. CO,; t.he water was lost. -Calculated. Found. 1. C .... 72 .. 29-51 28-78 H, .... 12 .. 4.92 Br .... 160 - .. 65-57 c___ 244 100~00 whichleaves no doubt as to the nature of the compound. More-over the slight deficieiicy of carbon was due to a trace of bro- mine-substitution for at the end of the treatment of the olefine with bromine the escape of a trace of hydrobrornic acid was not iced. To resume. Melampyrin free from maniiite is resolved by liydriodic acid iuto iodide of hexyl accordiiig to the equ nt'ion C6~18(HO(6+11HI= C6H131 + GH,O + Ilo.The carbon-condensation of melampyrin is therefore the same as that of mannite. Identity between the two bodies we do not contend for; on the contrary thcrc is a difference in the readi- ness with which the rzaction of hydriodic acid may be accom-plished. Mannite is at tacked very readily malampyrine with greater difficulty. A way of explaining the difference by means of formulae is by writing the peroxide of hydrogen in different places in the two bodies thus C6H8 (Ho)6 ; c (H0)6N We do not insist upon this mode of interpretation; it is only one possihle method among many. We hope in the course of a short time to be able to pub- lish an account of the various mcmbers of the sqar and mannite group. The following substances; we hope will be ready very soon.1. Dulcite. 5. Sorbite. 2. Phycite. 6. Quercitc. 3. Ery th romanni te. 7. Glycogen. 4. Inosite. The foregoing paper mas nearly finished wheu we red that TIiE CONSTITUTION OF MELAMPYl3IN. M. V. de Lugnes had applied our method to the investigation 6f erythromannite. This body is particularly interestiiig inas-much as it is believed to bc a rnannite having the formula C,H,,O, which should yield iodide of tetryl on treatment with lrydriodic acid. From M. de Luynes' communication which appeared in the Com,ptes Rendus (Oct. 13 1862) it seems that he boiled erythro- mariiii tc with hydriodic acid when LL licnvy oily liquid distilled. This liquid separated from the water was redietilled several times and then purified from excess of iodine by means of an alkali aud dried when it boiled at 120"C.and had the composition of iodide of tetryl. We cannot pass over this notice without remark- ing that it seems to us to be strange that M. de Luynes' iodide would bear the treatment to which he subjected it. Iodide of hexyl obtained from mannite would be utterly destroyed by such management ;for we find that even when freed from iodine the crude product decomposes at low temperatures evolving volatile liquids. It must be first distillcd with water in a stream of car-bonic acid; it then becomes pure and colourless and may be dried and distilled alone without decomposition. We necd hardly remind M. de Luynes that if the decomposition of which we speak did actually take place the agreement of his analysis with the cornposition of iodide of tetryl or of any other iodide must be regarded as accidental and as establishing nothing at all.It is a pity that M. de Luynes did not obtain any derivative from his iodide. If he had sufficient material at command to determine the boiling point of the iodide he must have had enough to obtain tetrj-lene by the action of alcoholic solution of potash. When he resumes his investigation we would recom- mend him to try to get tetrylene and make the bibromide from it. As M. de Luynes announces his intention of trying to get the other terms of the series from his iodide of tetryl we will antici-pate a portion of our history of the hexyl-compounds which we have promised to publish when our research is tolerably complete.Hexyl-alcohol may be prepared by heating iodide of hexyl with oxide of silver and water. There is produced at the same time a considerable quantity of hexylene (boiling point 70° C.) and also of another liquid of very high boiling point most probably a parahexylene. TOOKEY ON THE SDPARA'L'ION OF The alcohol aftcr rcpcntcd rcctifications boils collst:\l\tly at 136' C. It is tlicrcforc al)immnl fbi*1;?1'C. is tlic hoiliiig point of tlic iiornid nlcoliol. Its spccific grayit? at O" C. is .HX~;it IIW a fisngrallt sIIicI1 ill watw. \-cry Iiiililic that of ainyl-:ilcoliol. It is iiisolul~l~ Misctl with wiicciitratcd siil1)liiirir acid at Oo(1 it yicltls pa~*;t-11c~sylc iiv ant1 110 tracc of' licly 1-sii 11)li nric acid.We would paiticalarly draw attelltion to the fact that ioclitlc of liesyl tends to split up iiito liexylciie and hpctrioclic acid uhcn any attempt is made to obtaiii compound ethers from it. With aqueous solution of caustic potash iodide of licxyl tnap he boiled without decoinposition. Wit11 alcoholic potash or sodiiiin-alcohol it gives hesyleiie. With acetate of lead or with oxalate of silvcr it gives a considerable quantity of hexyleiie whether tliere is formed acetic or oxalic hexyl-ether as a bpe-product we have not yet established but we suspect it. Heidelberg October 21,1862.

ISSN:0368-1769    

DOI:10.1039/JS8621500456

出版商:RSC    

年代:1862

数据来源: RSC

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TOOKEY ON THE SDPARA’L’ION OF L1V.-On the Separation of Tin from Antirnon?y and on the Analysis of Alloys containing Lead Tin Antimony and Copper. BY CHARLESTOOKEY, F.C.S. Of the Metallurgical Laboratory Royal School of Mines THEseparation of tin from antimony with a view to their direct quantitative estimation has hitherto been regarded as an analytical process involving considerable difficulty on account of the similarity which exists in the behaviour of the compounds of those metals with reagents. The method proposed by Gay Lussac consists in precipitating the tin and antimony together by means of a strip of zinc; the weight of the precipitated metals having been ascertained they itre then redissolved in nitro-hydrochloric acid and the antimony TIN FROM ANTIMONY ETC.463 scparated from the diluted solution by a strip of tin the amount of' this metal origirially associated with the antimony being estimated hy difference The more reccnt method by Rose provides for the direct estimation of each metal the separ at'ion being cfl'ccted l~yfusing the oxides with hydrate of soda aud cligcsting the antimonate and stannate of soda produced with dilutcd alcohol the insoluble antimonatc of soda heing afterwards washed on a filter with alcohol of increased strength as the opcrntion of washing a1)proaches completion. Having had occasion to examirie some alloys containing lead tin arid antimony with small quantities of copper and having failed to obtairi suficieiitly accurate rcsults in the separation of tin from antimony by eitlicr of the processes mentioned I made several attempts to efwt the objcct in view but without success when the rcactiori betwecri the sulpiiides of tin mid antimony and hydrochloric acid (gas) occurrctl to me as likely to afford a method fyce from ohjcction.IVlieri tersulpliide of antimony is cxposcd to the action of hydrochloric acid (gas) decomposition is effected at the ordinary tcmperature vith production of sulpliide of hydrogen and ter-chloride of antimony which xlieri gently heated is easily iwlatilized in a current of the gas. Protosulphide of tin Then treated in a simiIar manner is also clecomposed the products of decomposition being sulphide of Ii~drogc~i and proto-chloride of tin icliicli may be licatetl to incipient fusion in an atmosphere of Iiydrodiloiic acid without undergoing any further change.A iicccssary coliclit ion therefore to tlic success of a separation by iiieatis of tlic rcactions just stated \rould be that the tin should exist in solution in the state of protoside. By tlie method of analysis to be further dcscrilml tlie tiii was obt:tiiieill in the state of' hichloride and in endeavouring to efk'ect the reduction of the bichloride to tlic state of protocliloride an esprinient was made to ascertain the action of metallic iron upon the niised chlorides of tin and antimony in presence of an excess of hydrochloric acid the result of which mas that while tlie hichloride of tin was reduced to protochloride the wliolc of the antimony appeared to be separated in the metallic state.Gmelin states on the authority of Fischer that iron does not precipitate tin from tlie protochloride at the boiling heat. To see how nearly separation could be effected by iron in the presence of OM TOOKEY OX THE 8EPARBTJOX OF hydrochloric acid 6.03 grs. of pure antimony and 4.16 p.of tin were dissolved in hydrochloric acid with addition of a few drops of nitric acid; the solution was diluted with water and after adding more hydrochleiic acid digested at a gentle heat with 15 grs. of thin sheet iron until thc whole of the iron was dissolved ; a considerable quantity of cold water was then added and the antimony collected on a weighed filter after being washcd with water and dried the antimony weighed 6-02grs.In a second ex- periment '3.145grs. of pure antimony and 1.065 grs. of pure tin were dissolved as before; thc antimony in this case after drying weighed 9-18 grs. the tin was precipitated from the filtrate by aulphuretted hpdrogcn tha protosulpliide of tin dried and converted into binoxidc by careful ignition the amount of binoxide obtained was 1.36 grs. containing 1.069 grs. of metallic tin. In the analyses of the alloys containing lead tin and antimony with small quantities of copper the ordinary method for separating tin and antimony from other metals was used viz. oxidation with nitric acid the action being promoted by heat and the excess of acid expelled by evaporation the nitrates of lead and copper were removed by washing on a filter with hot water.By pro-ceeding in this manner it was found in two analyses of the same alloy that the amounts of lead and also the collective weights of the oxides of tin and antimony differed to a considerable extent. The same discrepancy was observed whether the acid used for oxidation was in the concentrated state or previously diluted with water. In order to ascertain the source of error the oxides of tin and antimony were examined and found to contain oxide of lead in a state of combination in which it could not be separated by washing with water and to aee whether the application of heat affected the result two equal weights (10 grs.) of the same alloy were taken one was treated in the usual manner heat being applied to promote the oxidation by nitric acid the excess of acid being expelled by evaporation; boiling water was then added and after perfect washing the mixed oxides weighed on ignition 8.92 gre.The other was oxidized by nitric acid withont the applica- tion of heat and the resulting oxides weighed 9-31grs. The application of heat causes therefore a large proportion of the lead to remain with the oxides of tin and antimony. When an alloy of lead and antimony is heated with nitric acid the TIN PBOM ANTIJIONY ETC. latter metal is converted into antimonic acid which combines with the oxide of lead the resulting compound being insoluble in water. That the whole of the lead might be separated from the other metals the following process was employed.The alloy was oxidized by nitric acid but little more acid being used than was necessary for oxidation; after removing the excess of acid by evaporation at a low temperature the residue was digested with hot water the oxides of tin and antimony being collected on a weighed filter and aftcr perfect washing dried at 110-120° C. After ceasing to lose weight,. they were carefully transferred to a glass boat; the filter with the small portion of oxides still adhering to it was again dried and weighed the difference between the two weights giving the amount of oxides operated upon. The boat was then placed in a condensing apparatus through whioh a slow current of hydrochloric acid was transmitted and wheu the contents of the boat had becomeliquid fiom the absorption of gas a gentle heat was applied in order to distil over the chlorides of tin and antimony.When the distillation was nearly finished a greater heat was used to expel the last tpces of hichloride of tin and the tube having cooled the boat was withdrawn and its contents (chloride of lead) dissolved out and added to the solution containing the nitrates of lead and copper. These two metals were determined as usual the solution being evaporated nearly to dryness with a slight excess of sulphuiic acid thc sulphate of lead washed with water acidified with sulphuric acid and the oxide of copper precipitated from the filtrate by a solution of potash. The chlorides of tin and antimony were poured into a small beaker ;the apparatus rinsed out with dilute hydrochloric acid and after adding more hydrochloric acid the solution was heated gently and digested with metallic iron (as pure as possible) until the whole of the iron had dissolvecl cold water was then added the antimony collected on a weighed filter and after mashing with cold water dried at 110" C.The filtrate from the antimony if not sufiiciently dilute was mixed with water and then saturated mith sulphuretted hydrogen. The salphide of tin being afterwards converted into binoxide by ignition. In order to simplify the process as much as possible the following plan was eventually adopted. Ten grains or more 466 TOOKEY ON THE SEPARATION OF TIN ETC. of the alloy to be analysed were introduced into a small piecc a of apparatus having the following form sufficient nitric acid to com-plete the oxididation was poured upon the alloy by means of a funnel-tube ; the end a was corked and the oxida- tion effected at a moderate tempera- ture.When the alloy had been con- verted into a perfectly white mass the excess of acid was expelled by attach- ing a tubc and cork to CL and causing a gentle current of air to traverse the apparatus either by meam of an as-b pirator or a pair of bellows; during this operation the apparatus should be heated sufficiently to cause the evaporation of the excess of nitric acid. The end a was tiow connected with an apparatus for genrrating dry hydrochloric acid (which should be made from fused chloride of sodium arid sulphuric acid) while the end b was immersed in a small quantity of water contained in a beaker ;the remaining part of the operation may be conducted as in the former process care being taken not to distil the volatile chlorides too rapidly and to avoid the fusion of the chloride of lead until all the bichloride of tin has been expelled.The iron employed to precipitate the antimony should be in the form of thin sheet about three times the weight of the antimony present being usually sufficient for complete precipitation. It is necessary that the flask for generating the hydrochloric acid be provided with a funnel-tube dipping just below the surface of the fluid in order to prevent the too rapid absorption of the gas by the water which is used to condense the chlorides of tin and antimony.

ISSN:0368-1769    

DOI:10.1039/JS8621500462

出版商:RSC    

年代:1862

数据来源: RSC

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HEINTZ ON DRPOBIT IN HEALTIIY UIUNE ETC. 467 LIT.-On the Composition of the Ainorplious Dt.p~~il in Healthy Urine. BY Professor IIEINTZ,of Hallc. [Cornmunicatcd in a lcttcr to Dr. Bcncc Jones l!’.C.S.] INyour paper on (‘The Composition of the Amorphous Deposits in Healthy Urine,” at page 213 vol. xv. of the Journal of the Chemi- cal Society you state tliat I consider the deposit as a mixture of different acid urates modified in form by the presence of other substances in the urine. I have nowhere said this. You will find my opiriion founded upon my experiments at page 238 of Muller’s Archives for 1845. I there say “It is therefore certain that the amorphous sediment always contains uratc of ammo-nia urate of soda and urate of lime and more rarely urate of potassa and uratc of magnesia;” and at page 260 “As I have already shown that thc fine amorphous sediment corisists of a mixture of urate of soda urate of lime and urate of magnesia and that it has riot only the same properties but the same com- position as the sediment prepared artificially the cause of the natural sediment being deposited as a fine amorphous powder be-comes very evident.This cause is the simultaneous precipitation of these three salts one of which the lime-salt as I have shown in a former part of the paper is always precipitated in the form of a fine amorphous powder whilst the ammonia-salt and the soda-salt when they are redeposited at the same time from a solution contain- ing common salt frequently fall as a fine powder ;but they more constantly form larger or smnllcr microscopic rounded masses.” You will see from this that I regard the simultaneous precipita- tion of the different uric acid salts as the cause of the formation of the amorphous deposit and I do not consider that it depends on the presence of other substances in the solution.I must add however that the misunderstanding you have fallen into is partly my own fault inasmuch as I have not sufficiently distinguished in my paper the two kinds of amorphous sediments which are met with in the urine. In the introduction I have only separated the crystalline sedi-ment from the amorphous; although farther on I have divided 468 NICHOLEON ON A VOLUBIETRIC PIIOCEGS the latter into the fine granihr dcpcsit cady soluble in warm water md the larger rantided deposit which is vith difficulty dissolved in warm watcr.This last form I hare oftcri produced artificially when only the uratcs of soda and nnimonia were lxescnt vliilst I olltainccl tlic fiiicr granular form with certainty 01dy when limc was prescnt. T therefore statcd that the presence of' limc mas necessary for the formation of the fine granular aniorplious (lcpoait of iimtes. As osalate has been so frcqucntlg found in the sediments of urine subsequently to the date of my experiments it might be thought that the lime which I obtained came from this source; but in opposition to this I must say first that I sometimes filtered the fresh niatlc urine before it gave the deposit of urates and at other tinies that I redissolved the amorphoiis deposit filtered it and then took the sediment which fell on cooling for cxarnination and that then I always found linic present; and secondly that in forming artificially the fine aniorphous deposit the presence of lime m-as always necessarj.But as you have found no lime in the sediments which you examined it is evident that my conclu-sion that lime is atbsolutclp necessary for the formation of the fine amorphous deposit of urates must be limited. The sediments which you examined contained much potassa and I found it only rarely and then in very small quantity I therefore made my experiments on the artificial production of the anlorphous sediments with fluids free from potassa and under thesc circumstances I found that it mas essential that lime should he present. I must therefore restrict my conclusion thus that for the formatioil of the fine aniorphous powdery sediment lime must Ee prescnt if potassa is absent.

ISSN:0368-1769    

DOI:10.1039/JS8621500467

出版商:RSC    

年代:1862

数据来源: RSC

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468 NICHOLEON ON A VOLUBIETRIC PIIOCEGS LVI .-On a Volzmelricnl Process for the Analysis of Waters. BY EUWARD F.C.S. Staff Assistant-Surgeon. NICHOLSON THEwant of a process by which surgeons and other scientific men interested in hygienic matters could easily make an analysis of' water has long been felt; and attefnpts have several times been made to supply the deficiency. FOR THE ANALYSIS OF WATERS. Professor Clark of Aberdeen indicated the titlcture of soap as a test for the presence of earthy salts in water; he adapted a burette with a special graduation to the determination of the hardness of water by the tincture of soap and drew up a table for calculating the amount of the different earthy salts corres- ponding to the quantity of soap decomposed by the water.The beautifill experimeuts of Professor Clark after somc examination and criticism by Professor Play fair Ur.Campbell and others was adopted by MIX. Boutron-Chalard and F. Boudet as the basis of the so-called ‘‘ Hydrotirn6tri6,” for which a prize of 2,000 francs was awarded them by the Academy of Sciences. These chemists adapted the soap solution of Pro-fessor Clark to a more complete determination of the earthy bases and as their very useful method’ has been ,used to some extent in France and is employed iu the Hygienic Laboratory of the Army Medical School at Fort Pitt I will give a brief outline of the process they employ. The solution of soap employed by MM. Uoutron-Chalard and Boude-t is of such a strength that 23 degrees of their burette (equal to 2.4 c.c.) form a permanent lather on agitation with 40 C.C.of a solution of chloride of calcium containing 0.25 grm. per litre. One degree is deducted for the excess of soap-solution requisite to form the lather significative of the termination of the reaction. These 22 degrees correspond then to 001grm. of chloride of calcium or to a quantity of any other koap-decomposing substance varying according to the relation of its equivalent to that of chloride of calcium. The number of degrees of soap-solution decomposed by 40 C.C. of a water when multiplied by certain factors given in a table gives the amount of chloride of calcium or of any other salt .dlibitum contained in the water. The operations for the analysis of water by this method corn-prise the following determinations :-1.The hardness of 40C.C. of water; this hardness is caused by carbonic acid gas lime magnesia and whatever iron and alumina may be present. 2. The hardness of 40 C.C. of water from which the lime has been precipitated by osalate of ammonia ; this gives the hardness caused by magneiia and by carbonic acid gas. 3. The hardness of 40 C.C. of the mter from which carbonate of lime and carbonic acid gas have been expelled by boiling; this permanent hardness after a deduction of 3 degrees for carbonate 470 NICHOLSON ON A VOLUMETRIC PROCESS of lime still remaining in solution is owing to salts of lime other than carbonate and to salts of magnesia. 4. The hardness of 40 C.C.of the boiled water from which the permanent lime has been precipitated by osalate of ammonia ; this gives the magnesian hardness. 5. The sulphuric acid is estimated by adding to 40 C.C. of water a measured quantity of solution of nitrate of baryta of known hardness; the hardness of the mixture is determined and the loas of hardness indicates the hardness of the sulphuric acid contained in the precipitated sulphate of baryta. The distinguishing features in this improvement of C1 ark’s process are the estimation of the permanent lime and magnesia salts and of the sulphuric acid. This easy method of estimating the more important constituents of water render this process most valuable in the economical analysis of waters as a means of determining the effect of a water on steam boilers and in domestic operations and also as a method for calculating the exact amount of lime that must be added to water to eliminate the carbonic acid and carbonate of lime.But apart from its economical value considering the process in the point of view of chemical analysis it is liable to some objections and appears susceptible of certain improvements. Two of the determinations are made after the addition of oxalate of ammonia ;and I find that this introduces a possibility of error since the oxalate of ammonia when added even in small excess either gives a peculiar hardness of its own or else deranges the production of a lather so as to render the result uncertain. It is also impossible to express the exact coiistitution of the solid ingredients of the water or give any precise idea of their com-position.No account is taken of the alkaline salts aid thus the advantages of the method are not fully brought out. Impressed with the delicacy of the reaction given by the solution of soap with the minutest quantity of earthy base or of carbonic acidgas (-00002 grm. of lime will cause a detectable hardness of 1-7th of a degree) I have endeavoured to adapt thin delicate test to a more complete and reliable method of volumetrical analysis; and I believe I have succeeded in bringing the process of MN. Boutron and Boudet by several modifications arid additions to an exactitude which leaves little to be desired. I have also simplified the calculations so as to render them even easier than those necessary in ordinary gravimetrical analysis.FOR THE ANALYSIS OF WATEIiS. 471 The burettes employed are divided into teiitlis of cubic eenti- metres or degrees each 0.1 C.C. Z= lo. Thcsc with two pipettes of 10C.C. nrtd 50 C.C. respectively n few basins and beakers a fern three-ounce stoppered bottles and a graduated liti*c-rne:~sui*c form a11 the apparatus rcquircd. The following solutions are employed as test-fluids :-1. An Alcoholic Solution of Soap.-The solution employed by MM. Boutron and Boudet is made with hard Marseilles soap and in consequence it is solid at ordinary temperatures. This is a great inconvenien'ce from the necessity of heating the test-fluid ; but after experimenting on a considerable number of soaps Dr.Parkes has found that the soft potash-soap of the London Pharmacopoeia is the best ; and this has accordingly been used by me. The solution is made by dissolving the soap without heat in a mixture of equal weights of alcohol and water. The soap-solution is made of such a strength that 20 degrees (2c.c.) are exactly equivalent to 50 C.C. of a water containing 0.1 grrn. per litre (or 7 grains per gallon) of carbonate of lime and on adding to 50 C.C. of such a water 22 degrees a permanent lather is produced by agitation. This requisite excess of 2 degrecs per 50 C.C. is to be deducted from all determinations of hardness. 2. A solution of nitrate of baryta containing 0.26grm. per litre and equivalent in point of hardness to the aforesaid staqdard water containing 0.1 grm.per litre of carbonate of lime. 50 C.C. of this solution mark 20 degrees. 3. A stronger solution of nitrate of baryta is usually employed ; it contains I *300grm. per litre ; 50 C.C. of it mark 100 degrees. 4. A solution of nitrate of silver containing 8.500 grm. (& of the equivalent of the salt) per litre. 5. A solution of oxalate of ammonia containing 0.355 grms. (d5of the equivalent of the salt) per litre. 6. A solution of permanyanate of potash containing 0.159 grm. of the equivalent of the salt) per litre. The above graduation of the solutions has been adopted as the important advantage is thereby obtained of being able to calculate the quantity of any substance per litre of water by multiplying the number of degrees obtained by the atomic weights of the substance.Thus-20 degrees x 50 (eq. of Ca0.CO') = slOOO grm. per litre of carbonate of lime 20 degrees x 28 (eq. of CaO) = *0560 grrn. per litre of lime. 20 degrees x 365 (eq. of Cl) = *0710 grm. per litre of chlorine. NIcrIoLsoN OR A VOLUMETRIC PROCESS Tlie Quantities thus ohtained when multiplied by 70 shorn tlie number of grains per galloii of water. The Analytical Process. 1. 50 C.C. of the water to be analysed are measured by the pipette into a stoppered bottle of about three-ounce capacity. The soap-solution is gradually dropped in from the burette the bottle being strongly shaken at intervals until a lather begins to form on the surface. The soap-solution is then added more cautiously and enough has been added when the water on agitation pe- serits an iridescent large-bubbled lather breaking down very slowly and a€ter a few minutes leaving the surface perfectly covered with a beady film reconvertible into a lather on again agitating.After a little practice the exact point where the lather becomes permanent is attained by the addition of one small drop about one-sixth degree of soap-solution. Tlie process thus indi-catcs the preseiice of *0005grm. per litre of lime. Two degrees arc deducted for the excess necessary to produce a lather. The number of degrees found represents the hardness due to lime magnesia iron and carbonic acid gas. The alkaline salts usually found in water have no effect on the soapsolution.* 2.The amount of lime and magnesia and by difference of frce carbouic acid gus is found by takiug the hardness of the water after expulsiou of the carbonic acid gas. To this effect 50 C.C. of the water are evaporated to dryness with one or two drops of sulphuric acid arid the residue is ignited to expel excess of acid; if tlie vapours be offensive the residue may be neu-tralized by a few drops of ammonia before ignition. The residue is dissolved in 50 C.C. of distilled water and the hardness is ascertained. Oxide of iron will remain insoluble ; its amount is to lie deducted from the carbonic acid. 3. The lime is determined by the well-known application of permangaimte of potash to the oxidation of oxalic acid. To 50 C.C.of the water add 50 C.C. (or if the hardness exceeds 50 degrees 100 c.c.) of the standard solution of oxalate of am-monia let the mixture stand in a warm place for an hour and filter. Tbe filtrate and washings are heated in a basin to about 70"C. * If the hardness exceed 80 degrees or if much magnesia be present the earthy soap often amumes a curdy form deranging the production of a lather; in this case only 25 C.C. should be taken for experiment the 50 C.C. being made up with distilled water. FOR THE ANALYSIS OF WATERS. with a few drops of hydrochloric acid and the standard solution of pemanganate of potash is added from a burette. Subtract the nuinber of cubic centimetres of permauganate required for oxida- tion of the excess of oxalic acid from the number of cubic centi- metres of oxalate of ammonia added to the water the difference gives the number of degrees of lime.50 C.C. of the permanganate-solution ought exactly to oxidise 50 C.O. of the oxalate of ammonia-solution. 4. Determinution of the Alkalies.-The amount of lime and magnesia once obtained by the processes described the ordinary process of estimating the alkaline salts by evaporating a certain quantity of the water with sulphuric acid and weighing the resulting sulphates is much facilitated. The lime and magnesian hardness have merely to be multiplied by the equivalents of sul-phate of lime and of sulphate of magnesia and the numbers thus obtained to be deducted from the amount of mixed sulphates per litre of water.I have however devised the following method for the volumetrical determination of the alkaline salts :-To 50 C.C. of the water ignited with sulphuric acid as before described (2),* add 20 c.c. or more of the stronger solution of nitrate of baryta taking care that the hardness of the quantity added (2 degrees per 1 c.c.) be much greater than that of the water as previously ascertained. If no alkaline sulphates are present the amount of sulphate of baryta precipitated will be exactly equivalent in hardness to the amount of earthy sulphates; and the hardness when ascertained by the soap-solution will be exactly that of the baryta-solution added. If for example 20 C.C. = 40 degrees of baryta-solution have been added to 50 C.C. of water containing 35 degrees of sulphate of lime and of mag-nesia (total 4dl + 35) 35 degrees of suiphates of baryta will be precipitated and the hardneas will be reduced to 40 degrees exactly the hardness of the baryta added.But on the other hand if sulphate of soda be present in the water in addition to the earthy sulphates a greater quantity of sulphate of baryta will be precipitated and the hardness will be reduced to less than 41)degrees. Should it be reduced to 36 degrees that will show that 4 degrees of alkaline sulphate were present.t It may be as well at process No.2 to evaporat 200 C.C. of water with sul-phuric acid diseolve the ignited residue in 200 C.C. of distilled water and take 60 C.C. for analysh. t If 20 C.C. of bsrytm solutionhave been added the excess of Soap-solution,to form NICITOLSON ON A VOLUMETRIC PROCE69.5. The chlorine is determined in 50 C.C. of the water by the so-lution of nitrate of siIver. If the quantity be very small it is best to evaporate 500 C.C. 04 water to a small bulk and count cubic centimetres as degrees. 6. The sulphuric acid is determined by adding to 50 C.C. of the water 10 c.c. or more if necessary of the stronger baryta-soh- tion and ascertaining by the soap-solution the hardness of the mixture. The 1093 of hardness from the precipitation of sulphate of baryta gives the number of degrees of sulphuric acid. 7. Iron is determined in the usual manner by the permanganate of potash solution. 500 C.C. of the water are evaporated to a small bulk with hydrochloric acid; the iron is reduced by sulphurous acid and estimated by the permanganate of potash solution.Ten cubic centimetres are counted as one degree of Fe203. If silica be present it will remain on redissolving the ignited sulphates and if 200 C.C. of the water have been evaporated with sulphuric acid it may beestimated by weighhg. In process 2 the oxide of iron becomes insoluble and increases the amount of carbonic acid gas from which it must be deducted. All the processes here described are of very easy execution. The method of estimating carbonic gas is unequalled in exactness and facility of execution by any method I know and the process for esti -mating the total capacity of saturation of the alkalies is extremely exact and satisfactory.The estimation of sulphuric acid devised by M.M. Boutron and Boudet is likewise of great precision. I append examples of the calculation of an analysis performed by this procesg to show the advantage obtained by the method of graduation I proFDse in establishing an empirical formula for the salts contained in waters. I. AnalyAe of the Water supplied by the Chalham Water Compatzy to Fort Pitt. Degreee. Carbonic acid gas* Calcium.. ...... 1. Hardness .............................. 63O.7 Mafiesim .... {Iron .......... Calcium ........ 2. Hardness ahr ignitionwith sulphuric acid . . 49O.7 { agnesium .... 3. Calcium ascertained by permanganate .... 48O.8 Calcium.. ...... a lather wiil be greater;2.8 degrees must be deducted.But it is perhaps better always to add 60 C.C.(100 degrees) of baryta. The deduction is then 4 degrees and the loss of hardness on 100 degrees ie the amount of alkali. The ixon ita to be deducted from the gross carbonic acid 4 degrees. FOR THE ANALYSIS OF WATERS. 475 Degrees. 4. Hardnees after ignition with sulphuric acid, solution and 60 degrees of blrryta added} 630.6 (sodium lm6e,4) 6. Chlorine ................................ 6O.5 ................ 6. No sulphuric acid ........................ ................ 7. Iron .................................... o0;2 ................ Deduction of an Empirical Formula for the Salts contained in the above Water. This calculation so tedious by the ordinary method becomes here of extreme simplicity.I combine the 5.5 degrees of chlorine with an equal number of degrees of sodium a balance of 09degrees of sodium is left. This with the calcium and magnesium is calcu-lated as carbonate. Deg. Equivs. Qrm. pcr litre. Qrs. per grl-Carbonate of lime .. 48.3 x 50 = -2415 x 70 = 16.905 Carbonate of magnesia 1.4 x 42 = *0058 x 70 = 406 Carbonate of soda.. .. -9 x 53 = ~0047x 70 = 0329 Chloride of sodium . . 5.5 x 58.5 = -0321 x 70 = 2.247 Oxide ofiron.. ...... -2 x 80 = -0016 x 70 = *112 Silica ........................ = -0020 x 70 = -140 -2877 20.139 Carbonic acid gas.. .. 3.8 x 44 = -0167 = = 2-52 C. (2C02) 8.93c.c. in per gal. Residue on ignition. ............... -2810 = 19.68. 11. Waterfront a pump at Fort Yitt.Degrees. Total liardries ...................... 56.8 Calcium and magnesium ............... 21.0 Calcium ............................ 16.9 Sodium ............................ 5.0 Iron (FeW) ........................ 1.2 Sulphuricncid ...................... 4.8 Chlorine ........................... 3.6 Dcgreeu. Cfrm. per Grains litre. per gal. r= Carbonate of limc ............ 1G.9 x 50 ,9845 x 70 = 5.915 Carbonate of magnesia ........ -7 x 42 = -0029 x 70 = -203 Carbonate of iron ............ 1.2 x 116 2(Fe0,C02) = '0139 x 70 = '973 Sulphate of magnesia.. ........ 3.4 x 60 = *0204 x 70 = 1.428 Sulphate of soda.. ............ 1.4 x 71 = *OO99 x 70 = -693 Chloride of sodium.. .......... 3.6 x 58.5 = *0210 x 70 = 1.470 -1526 10.632.Carbonic acid gas ............ 14.6 x 41 = -0642 =31.3c.c.pr.lit. (x -537) (31.3c.c. x 4.54 x .OG1) Solids by evaporation -1500 per litre. =8%7c. in. per gallon. I may mcntiori that tlic solution of' pcrinaiiganatc of potash of tlie standard liere empioycd mswc'rs ndinirnbly for the csti-mation of organic inattcr iii water. 500 C.C. of water arc hcatccl to 7OoC. with a few drops of piirc sulpliuric acid and tlic standard soliitim is added I C.C. :kt a timc until a colour lasting for 10 minutes is obtained. Evcry 10 C.C. of test-solution thus de- colorised is cqid to oiic degrec of organic matter requiring onc equivalent of oxygeii for complete oxidation (corresponding to C203,H0,far example). I may say a few words as to the best mauner of attaining the rapidity wliicli forms one merit of this process.I first sct 200 C.C. of water to evaporate with a few drops of sulpliuric acid for processes 2 and 4; I also precipitate the lime in 50 C.C. for process 3. By the timc I 1i:wc taken the total hardncss and estimated tlie chloriiie su1l)liuric acid and iron tIic evaporation is finislied and the resicluc ready to bc talcen in hand. Two or thee analyses can thus be easily lierforiiicd in a clay. Oric point must be carefully observed that tlie distilled water contain 110 carbonic acid gas. The delicacy of the soap-test for this gas is so great that the distilled water will speedily acquirc one or two degrees of harclness if left exposed to thc air. If it 11~s acquired any hardness from this cause it slio:ild be boiled previously to use.In coiiclusioii I must beg to acknowledge my obligations to Dr. Parkes who by liis discovery of tlie fact that contrary to expectation potash-soap might be employed to maltc ;L soap so-lution perfectly fluid at ordinary temperatures removed what mould have been an insuperable liar to any perfection of the method of analysis.

ISSN:0368-1769    

DOI:10.1039/JS8621500468

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

DANCEIi ON IIYI’OB110310US ACID LV 11.-On Hypobromous Acid. BY WILLIAM DANCER Dalton Scholar iu the Laboratory of Owem College Manchester. 13-4LA it D:I in liis original mcinoir on bromine publishcd in 1826 mentions that wlicn bromine water is brought into contact with tlic nlkalics arid alkaline earths dissolved or suspended in water tlie smcll and colour of the broniirie disappear whilst no oxygen gas is evolved and that on the addition of a weak acid to the solution bromine is liberated ; it reaction observes Balard which proves that bromine forms with these oxides a compound analogous to the so-called olilorides of lime and soda. Many other chemists csyecially Liiwig,t Fritsche,$ and Gay Lussac,§ mention the mode of preparing a bleaching salt of bromine with the alkalies indicating the existence of hypo- bromous acid; indeed Gay Lussac states that this oxide can tie obtsiricd in thc gascous state by the action of bromine on dry oxidc of mercury but Pelouze showed that the gas thus produced was oxygen.Our knowledgc concerning the properties of this oxide of bromiiic is howevcr very limited so much so that Rerzelius states that cven its existence is uncertain. At thc suggestion of Profcssor ltoscoe I undertook the iiivcstigation of this subject and I have succeeded in &tnblishing ilic composition of hypobronious acid in aqueous solution and in determining some of its properties. I hare however been unable to prepare tlie hypobromous aiihydridc as this body is far more unstable than the corresponding chlorine compound and when liberated in the gaseous form splits up even at the ordinrzry atmospheric temperature into bromine mid oxygen.In order to assure myself of the abseiicc of chlorine in the broinine employed the whole quantity of bromine was dried arid ilistillcd ; the first portion of the distillate was collected separately and a weighed quantity of this liquid reduced by aqueous sulphu- rous acid and precipitated as bromide of silver ; thus 2.3345grms. of bromine yielded 5.486 grms. of bromide of silver tlie theoretical Ann. Ch. Phya. xxxii. 337. .t Pogg. Ann. xiv. 14 485. $ J. pr. Chem. xxiv. 291. S Compt. rend. xiv. 961. I>.IKCER ON HYPOBROMOUS ACID. wciglit of silvcr- salt obtaiiia1)le froiu tlic abovc qimitity of hrotninc \icing 5-ltj7 grins.sccoiid analysis was mark 1)y passing dry cliloriiic gas 0x1'n ~~ciglicd portioii of bromide of silver olitaiiicd froill a siiiiilar qiiniitity cf bromiiic 2.291 grrus. of broiuitle of silvcr yicltlcd 1.735 griii. of' cliloritlc of silvcr a quantity closcly corresponding to tlic thcorctical amout of 1.751 grin. IIciicc wc may coiic.liicic that the lmmiinc cm-ploycd was frcc from clilorinc. I.-Action of Bronzine on Aqueous Solutions of the Salts of the Alkalies aitd Alkaline Earths. (1). On shaking a strong solutioii of hydrate of potash or soda with bromiue no bleaching cornpound is fonuecl bromide and bromate of potassium only being produced. (2). With IL \re& solution of hydrate of potash or soda a slightly yellow liquid is obtained which blcaches strongly ; this must con-tain (z compound of the alkali with hypobroruous acid as upon distillation either under the ordinary atmospheric pressure or iu vacuo the distillate does not possess bleaching properties and becomes sliglitly coloured with free bromine.(3). 011shaking bromine-water with solution of the carbonate of potassium or sodium carbonic acid is given off and the liquid which is of a light yellow tint bleaches vegetable colours. On being heated to 3OoC. or left for some time at the ordinary atmos- pheric temperature bromine is liberated and the solution becomes colourless losing its bleaching properties. (4). When an aqueous solution of phosphate of sodium is shaken up with bromine-water a bleaching solution is produced ; this however cannot be distilled even in vacuo without decornposi- tion free bromine being evolved.(5). Bromine shaken up with solution of chloride of sodium does not yield a solution containing hypobromous acid behaving with this salt unlike chlorine which according to Williamson yields a solution from which free hypochlorous acid can be obtained by distillation. (6). Solid hydrate of lime shaken up with bromine absorbs it with evolution of heat becoming coloured red. If a small quantity of water be added the mixture gradually loses its colour and gains the peculiar sweetish smell of' bleaching powder ; filtered from the excess of lime the solution has a light yellow colour and bleaches vegetable colours rapidly.DANCER ON HYPOBROMOUS ACID. This solution even when very weak is decomposed bj' dilute nitric sulphuric and hydrochloric acids behaving with these acids unlike the corresponding chlorine compound. Carbonic anhy- dride in excess when passed into strong solutions decornposcs this salt liberating bromine ; but when this gas is passed slowly into a dilute solution the hypobromous acid is not entirely de- composed for on distilling in 'uacuo the distillate was found to contain hypobromous acid as well as free bromine. (7). Bromine water added to baryta-water partially loses its colour and the solution possesses strong bleaching properties. A current of carbonic anhydride passed through the solution liberates bromine and after some time precipitates the barium as carbonate.Hence it is evident that bromine forms with baryta compounds similar to those which it forms with lime. 11.-Action of Bromine-water on Solution of Nitrate of Silver. When pure brornine-water is shaken up with excess of nitrate of silver solution a liquid is produced which bleaches strongly (Spiller *). This liquid on boiling yields a distillate of which the first portions contain much free bromine but the later portions possess a light straw-colour and still bleach vegetable colouring matters powerfully. If the distillation of the solution be con-ducted in vacuo under a total pressure of 50 mm. of mercury the liquid boils at 4OOC. ; and all the distillates have a straw CO~OU; they do not contain free bromine they possess an acid reaction and bleach strongly.If however the temperature rises to 6OoC. the dark-coloured vapour of bromine appears in the retort show- ing that at that temperature decomposition of the hypobromous acid ensues. For the purpose of determining the composition of the bleach- ing substance here present defiuite volumes (50 cbc.) of the almost colourless acid distillate were completely reduced with freshly prepared solution of sulphvrous acid and the excess of sulphurous acid was removed by rapid boiling. In one of the portions the sulphuric acid formed was estimated as barium-salt ; in the other the barium weighed as bromide of silver.? For every 233 parts by weight of siilphate of barium obtained the liquid contained 8 parts by weight of oxygen ; out of every 188 parts of bromide of silver found 80 parts of bromine were com- Chem.News 1 38. t According to the method proposed by Calvert and Davies for the adpie of hgpochloric acid.-Chem. SOC.Journ. vol. ii. p. 193. DANCElt ON HYP0131:03~OUS ACID. bined with this oxygen. Hence the relation between the quantities of bromine and oxygen in the compound is obtained. The folloffing numbers give the experimental results and show that bromine and oxygen are contained in the liquid in quantities represented respectively by the numbers 80 and 8 :-I.-50 cbe. of distillate yiclds 0.402 grms. BaS04 and 0.324 grms. AgBr. 11.-50 , , 0.222 , , 0.183 , 9) 111.-50 , 9) Oe4'7 9 0.321 , IV-60 , , 0.389 , , 0.323 , Hence-Calculated.Found. P A \ -I. 11. 111. IV. Br 80.0 90.91 90.90 91.07 90.53 91.13 0 8.0 9-09 9.10 8-93 947 8-87 -L___ --88-0 200*00 100~00 100~00 100*01) lOO*~O In order to determine whether half the total bromine in con-tact with nitrate of silver solution is converted into hypobromous acid two equal volumes of the same bromine water were tsken and in one portion the total bromine was determined after cam- plete reduction with sulphurous acid whilst to the other portion nitrate of silver was at once added and the precipitated bromide of silver was weighed. 1. 50 cbc. Bromine-water reduced with sulphurous acid yielded 1.206 grms. BrAg or 0.513 Br. 50 cbc. Bromine-water not reduced with sulphurous acid yielded 0.647grms BrAg or 0-275 Br.Hence 46.40 per cent of the total bromine was contained in the form of hypobromous acid and was not precipitable by nitrate of silver. 2. 50 cbc. Bromine-water reduced with sulphurous acid yielded 1.618 BrAg or 0.6885 Br. 50 cbc. Bromine-water not reduced with sulphurous acid yielded 0.957 BrAg or 0.4072 Br. Hence 40.88 per cent. of the total bromine was contained in solution as hypobromoiis acid. 3. 50 cbc. Bromine-water reduced with sulphurous acid yielded 1.205 BrAg or 0.5126 Br 50 cbc. Bromine-water not reduced with sulphurous acid yielded 0.642 BrAg or 0.273 Br. I-Ie:ic= 46-74! per cent of tlic total bromine was contained iu solution as hypobromous acid. On standing in contact with excess of nitrate of silver solution aqueous liypobromous acid is slowly decomposed and bromide of silver is precipitated; this explains the exccss of bromide of silver found in the unrcduced portions.From the above analyses it is iiowewr clear that the decomposition in question really occurs. On distillation at teniperatures above 60°C.,ayucous hypobro-mous acid is decomposed free bromine 1)eing liberated aud bromic acid formed. This is shown by the appearance in the retort of a difficultly soluble silver-salt which crystallised in long needles and was shown by analysis to be bromate of silver 111.-Action of Bromine-water on Oxide of Mercury. Hypobromous acid is likewise formed when bromine-water is shaken up with fiuely divided protoxide of mercury prepared either by igniting the nitrate or by prkcipitation with potash.After agitation for a short time with an excess of oxide of mercury the whole of the bromine disappears; no oxygen gas is evolved but the liquid assullies a light straw colour possesses the peculiar sweetish smell characteristic of hypobromous acid and bleaches strongly. This liquid when distilled under the ordinary atmospheric pressure undergoes rapid decomposition ; frce bro- miue is given off in large qriantities and bromate of mercury remains behind in the retort. Under a pressure of 40mm. of mercury when the liquid boils at about 3OoC. the aqueous hypobromous acid distils over undecomposed. By saturating aqueous hypobromous acid thus prepared with bromine shaking again with oxide of mercury and repeating these operations several times R more concentrated aqueous solution of hypobromous acid can be obtained; 100 cbc.of a liquid which had been thus treated six times was fouad to contain 6.21grms. of combined bromine in solution. It is not possible however to obtain a pure distillate from a liquid prepared in this way as the concentrated solution is decomposed even at 30" C. bromine being liberatcd in large quantities. That the hypobromous acid like the corresponding chlorine compound is not combined with the oxide of mercury is proved by the fact of its volatility. Owing however to the ease with which this body splits up into bromine and bromic acid the hypobromous acid obtainable in the distillate is not equivalent DANCER ON nYPOBROXOU8 ACID.to half the total quantity of bromine employed. In one experi-ment 1,000 cbc. of bromine-water containing 10-44 grms. bromine yielded on distillation only 2,818 grms. of bromine combined as hppobromous acid. In this respect then the lswest oxide of bro-mine differs from aqueous hypochlorous acid which as Gay Lussac showed may be distilled when dilute without any clecompositioii occurring. The first portions of the distillate contain however by far the largest proportion of the acid as is shown by the following determinations :-1 1,000 cbc. of bromine-water containing 16-88 grms. of bro-mine were shaken tip with oxide of mercury and the clear liquid distilled in vacuo at 30°C.,under a pressure of 40 mm.mercury. Successive volumes of ,the distillate amounting to 100 cbc. each were analysed with standard silver-solution after complete reduction with sulphurous acid. The 1st 100 cbc. contaiued 0.736grms. bromine. 2nd , > , O.ti60 , >> 3rd , , 9 0.404 9 , 4th , 9 > 0.304 9 , 5th , 9 >) 0.244 , , 6th ,> , ,> 0.174 , , 7th , I ,I 0.156 , J 8th , , , c"30 , JJ 2. 1,000 cbc. of bromine-water containing 10.00 grms. bromine treated with oxide of mercury and distilled gave the following results :-The 1st 100 cbc. contained 0.416 grms. bromine. 9, 2nd I J) 0*404 >> ,> ,9 J, 3rd 9 , 0-244) , YJ 4th > 9 0.124 ,J J> I# Mean of the 5th 6th 7th , , 0.113 9 ,7 8th , 0.024 ,t Y9 ,1 9 In order to determine the proportion of the total quantity of bromine which in contact with oxide of mercury and water formed hypobromous acid a solution of bromine-water containing in 25 cbc.0.2537grms. of bromine was shaken up with an excess of oxide of mercury until all the free bromine had disappeared; the solution was then filtered and the mercury in the filtrate DANCER ON HYPOIlBOMOUS ACID. estimated as sulphidc; 0.211 grms. of sulpliide of mercury cor-responding to O-14fiT> grms. hroniiiie mas obtained. In like maiincr tlic filtratc from 100 cbc. of a sccond portion of brolniric-water contaiiiirig 1-797 griiis. of bromirlc yicldcd 1.6365 grms. of sulphide of incrciwy corresponding to 1.128 grms. of bromine. IIeiicc it appcars that in tlrc one c'asc 42-61pcr cent.of thc total bromine was couvcrted into hypohomous acid and in the other case 37.22pcr cent. It is prolxhle that a soluble salt of mcrcury nnd Iiypobromous acid is thus forincd ; this supposition ~ould,at least account for tthc esccss of mercury found in the filtratc. The extremely unstable character of the aqueous hypobromous acid at the oriiinary atmospheric temperature is well shown by its behaviour with osidc of silver. IVkien brominc water is agi- tated with fincly divided oxide of silver in excess liypobromous acid is immediately produced and if the solution be quickly poured off from the excess of oxide and from the precipitatcd bromide which is formed it possesses strongly bleaching propertics ; but if it be allowed to rcmain even for a few minutes in contact with the excess of oxide of silver bubbles of Gsygen gas are given off bromide of silver is formed the solution bcmmes colourless and altogether loses its bleaching power.It is proliable that hypobro- mite of silver exists in this solution; for if the solution poured off quickly froni the excess of oxide of silver be allowed to stand for some time it is found to decompose bromide of silver being precipitated. IV.-Action of Bromine upon dry Oxide of Mercurp. On acting with bromine upon an excess of dry oxide of merciiry prepared by igniting the nitrate great heat is evolved; and if the mixture be heated in a sealed tube at 100"C. a dry powder is formed which possesses -the peculiar smell of bleaching-powder and when treated with water gives a strongly bleaching solution.No bleaching substance is however formed when an excess of bromine is employed a hard mass remaining in the tube but in both cases large quantities of oxygen gas are liberated causing the tubes to burst with a loud noise when the ends are opened with file. The mercury bromine and oxygen contained in a portion of the powder from one of these tubes were determined directly. (a). Determination of Bromine.-lo1295 grms. of the mass left in the tube was dissolved in nitric acid and the bromine pre- 1,ANCElI ON HYPOBROMOUS ACID. cipitntcd with nitrate of silver 0.7195 grins. bromide of silver was obtaiucd corrcspoiidiiig to :?7*111)cr ccnt. brominc. (b). Deteriitiiuifiou of Jl~l~.c~~~.~/.-1.133~ grms.of the same mixture mas dissolved ill liydrocliloric acid atid the mcrcury prc- cipitated by sulpliurctted Iiydrogcii 0.8975 grins. I-IgS was ob-tained correspciiding to 68.28per cent. mercuiy. (c) Determination of Om~gen.-0.9575 grms. of the mixture was placed in a coinbustion-tube closed at 0112 end containing some dry crtrbonatc of niangaiicse; after tlic air lid becri cs-pelled from tlie tube hy heating the carbonate tlic mercury-salt was hated aid tlic oxygen-gas collected over nicrcury ; the apparatus was again swept out by tlic carbonic acid and after this gas had been removed from the receiver by solution of caustic alkali the oxygen was trniisferred to a calibrated eudiometer for measurement care hciiig taken to ensure the complete removal of tlic carbonic acid by mcms of a potash ball.The volume of oxygen thus obtained rcduced to 0°C. arid 760 mm. Bar. amounted to 256 cbc. corresponding to 3.84 grms. in 100 grms. of the mixture. From thesc data the relatire quailtities of bromide of mercury oxide of niercury and hypobromite of mercury prescnt in the mixture can be calsnlatcd by the help of the three following equations :-Let x equal the per centage weight of HgBr in salt. Y > > > HgO 9) >J 9 jY ) HgOBrO (1). ++$ x -t ## y + +$-+z = 68-28 (2). 33% + ?&z = 27.11 (3). dx Y + +& 2 = 3-84! Or x = 48.62per cent. bromide of mercury y = 37.06 , oxide I z = 13.48 , hypobromite , Another portion of the bleaching salt was prepared and analysed as before.The following results were obtained :-(1). 0.869 grms. gave 0.3735 grms. BrAg = 18.29 per celit. bromine. D-INCER ON IIYPOBROBIOUS ACID. (2).0.871 grms. gnvc 0.7315 grnm IIgS = 74C4 per ccnt. rn crcury. (3). 1.688 gyms. %we 588.3 cbc. 0 at OOC. arid TG mni. = 5-00 per cent. oxygen. Hence by substituting these numbers in ihe foregoing equations we have-x = 31.50 per cent. bromide of mercury. y = 55.89 , oxide ¶ LI-10.54 , hypobromite 7 97.93 A portion of the contents of the tubes consisting of a hard solid mass was separated from the adhering powder and analysed. Tiiis as is seen by the following numbers consists of' a mixture of bromide arid oxide of mercury thc former existing as a white crust surrounding the latter the hypobromite in this portion having been probably decomposed either by the hat which was cvolvcd during combination or by an excess of bromine.(I). 1.8355 grrm. of thc salt gave 1.032 grms. BrAg comes- pontling to 23.92 per cent. of bromine. (2). 1.644 grms. of salt gave 1.389 grms. HgS corresponding to 72.85 per cent. of mercury. (3). 1.782 grms. gave 399.5 cbc. of oxygen at 0°C.and 76 mm. corresponding to 3.22 per cent. of oxygen. Hence it is seen that the solid substance consisted simply of a mixture of bromide and oxide of mercury in the following proportions :-Bromide of mercury = 56-26 per cent. Oxide , , = 40.36 , 102.61 V.-Attempts to Prepare Hypobromous Anhydride. All the methods used for obtaining hypochlorous anhydride fail when applied to produce the corresponding bromine com-pound.When dry chlorine is passed slowly over dry oxide of mercury gaseous hypochlorous anhydride is formed. When however the same reaction is repeated with bromine. no hypo- DANCER ON IIYPOBROMOUS ACID. bromous anhydriclc is fornicd osygen gas alone being produccd both at the ordinary atmospheric temperature at 100°C. and at minus 18" C. Wlieii bromine acts upon moist oxide of mercury no oxygen gas is evolvcd but the hypobromous acid is all absorbed by tlic watcr and if the mixture be heated to a tcinperature above 30°C. it is dccomposed bromic acid arid frec broniiiie being the products. Tlic iiwtliod uscd by Balard for preparing hypoclilorous anhy-dride by placing a saturated aqueous solution of the acid in a tube over mercury and absorbing the water with nitrate of limc or phosphoric acid does not give satishctory results with hypo- bromons acid for the strong aqueous acid is decomposed iii contact with the mercury and the gas which collects proves to be oxygen.The spontaneous decoinposition of gaseous hypo-bromous anhydride at the ordiiinry atmospheric tempcrature into bromine and oq-gen was slmwii in the following manner :-About two ounces of oxidc of mercury togctlier with six ounces of water mere put into a flask lialf an ounce of bromine was added and the whole well shaken up; as soon as the solution had lost its red colour another portion of bromine was added and it was again well shaken.This process was repeated (more oxide of mercury being occasionally added) until about five ounces of bromine had been used ; the liquid which did not smell of fiee bromine was then filtered and a small flask mas completely filled with it and this flask mas connected by means of a piece of caoutchouc tubing (containing a Bunsen-valve) with a large bulb blown upon a thick piece of glass tube ; the conncctioiis being made gocid the bulb was attached to the air pump exhausted and the tube sealed off hetween the hulb and the air pump. TVhen the valve between the exhausted bulb and the flask was opened gas possessing the colour of bromine was given off from the liquid even at the ordinary temperature. After a short time the bulb was opened under water no apparent absorption took place.Another bulb filled in a similar may was opened under mercury in a fen-minutes the gas became colourless and the mercury rose in the tube. An eudiometric analysis was made of the residual gas and the following results were obtained :- DANCER ON HYPOBROMOUS ACID. No. 1. Analysis of gas evolved at the ordinary atmospheric temperature and under reduced pressure. Vol. at 0" Volume of gas employed.. . . . . . . . . Ditto after addition of hydrogen . . Ditto after explosion . . . . .. . . . . . Vol. 206.5 311.9 246.2 P. 3325 438.5 362.0 Temp. and 76 mm. 18.5 80.63 14.8 165. 9 12'6 107' 3 The oxygen which remains after deducting the calculated quan-tity required to form air with the nitrogen present amounts to 3-26per cent.No. 2. Analysis of gas evolved at 25"C. and under reduced pressure. Vol. at 0°C VOl. P. Temp. and76Omm. Volume of gas employed.. . . . . . . .. 191.87 324.7 9'0 77.84 Ditto after addition of hydrogen . . 389.06 614.2 9 6 25010 Ditto after explosion . . . . . . . . . . 340.78 460.6 73 197-7 The surplus oxygen in this case amounts to 1.7 per cent. From this it is seen that the gas consisted of a mixture of air oxygen and bromine the two latter resulting from the decomposition of the hypobromous anhydride. VI.-Solu€ility of Bromine in Water. To the above experiments I have to add the following deter- minations of the solubility of bromine in water between 5" and 3O0C. The numbers in the first column of the following table give the temperatures at which the solubility was determined; the numbers in the secmd column give the weight of bro-mine in grammes contained in 100 grms.of bromine-water at the corresponding temperature as the mean of several estimation8:-n. 6°C 3*000 grms. loo 8-32? ,, 16" 3.226 , zoo 5.208 ,, 25" 3-16? ,, 30" 3 ,126 , DANCER ON IIYPOBBOMOUS ACID. By help of graphical interpolation the following numbers were obtained for the solubility of bromine in water between 5' and 3OoC :-Bromine i Bromine ii Bromine ii Bromine ir l'emp. 100 Bro-Femp. 100 Bro-Temp. 100 Bro-I'emp. 100 Bro-mine-wate mine-watex mine-water mine-water I 5°C 3.600 13" 3-269 21" 3,186 29" 3.136 6 3.536 14O 3.253 22' 3.179 30" 3.331 7" 3.474 15' 3.236 23" 3.173 8" 3-421 16" 3.228 24" 3-166 9" 3.376 17' 3-218 25O 8.159 10" 3 *336 180 3.208 26" 3.151 11" 3.313 19" 3.200 27" 3.146 12" 3.229 20" 3.192 28" 3.141 I

ISSN:0368-1769    

DOI:10.1039/JS8621500477

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

489 PROCEEDINGS AT THE MEETINGS OF THE CHEMICAL SOCIETY. January 16th 1862. Dr.Hofmann President in the chair. The following were elected Fellows of the Society :-John Attfield Esq. St. Bartholomew’s Hospital; J. Chris-ti an Esq. 11 Upper Copenhagen-street Isyigton ; John (3. Dale Esq. Foxhill Bank Church near Accrington Lanca-shire; Thomas L. Phipson Esq. The Cedars Putney; Charles ’ W. Quin Esq, 4 Norman-terrace Wellington-road Clapham ; Henry Rayner Esq. Messrs. Chance’s Chemical Works near Oldham ; Joseph Storey Esq. Chemical Manu- facturer Lancaster; Richard Wheeler Thomas Esq. 10 Pall Mall ; C. Greville Williams Esq. Glasgow. The following vote of condolence was put from the chair and carried unanimously :-r6 To the Queen’s most excellent Majesty “May it please your Majesty We the President,Vice-Presidents Council and Fellows of the Chemical Society beg permission to approach your Majesty and humbly express our great sorrow at the death of his Royal Highness the late Prince Consort who during his life evinced a warm interest in the progress of the science to which our labours are devoted.We pray that the consolation and support of Almighty God may be vouchsafed to your Majesty under this severe bereavement and that your Majesty may long continue to reign over your loyal and faithful people ” 4m PROCEEDING8 OF TRR CITEMTCAL ROCIETY. The following papers were read :-“ On the simultaricous variations of Hippuric and Uric Acids irl healthy Human Urine :” by Dr.H. Bence Jones. ‘‘On the solubility of Suiphatc of Lcad in Hydrochloric and Kitric Acids :” by Mr. G. F.Itodwell. . ‘(On a new method for effecting the substitution of Chlorine for ITydrogen in Organic Co~npounds:” by Dr. H. Muller. February Gth 1862. Dr. Franklnnd Foreign Secretary in the Chair. Mr. John Broughton St. Bartholomew’s Hospital; Dr. Alexander Martiuu and Dr. Geyger Royal College of Chemistry were elected Associates of the Society. The following papers were read :-I‘ On Ground Ice :” by Mr. Richard Adie. “ On Crystalline Xanthine in Human Urine :” by Dr. H. Bence Jones. I‘ On Silica :” by Mr. A. 131. Church. On the source of the Arsenic contained in Sulphuric Acid and on the preparation of an Acid free from Arsenic:” by Pro-fessor B 1 oxa m.I‘ On a deposit of Phosphate of Lime occurring in Teak-wood :” hy Mr. F. A. Abel. On the composition of the Water of certain Boiling Springs in New Zealand;” by Dr. J. Smith. Febniary 20th 1862. Dr. Hofmann President in the chair. Mr. Traugott Ludwig 7 Bury-court St. Mary-Axe was elected a Fellow. The following papers were read :-“Note on Professor Bollcy’s paper on some Physical Proper- ties of the Sllloys of Lead and Tin:” by Dr. RIatthiessen. PROCEEDTNGS OF TIIE CHEMICAL SOCTETY. 491 “On the quantitative dcterminatiou of thc Alkalies in Firc Clays and other insoluble Silicates :” by Mr. G. Gore. “ On the Coiistitutioii arid Artificial Ii’ornration of ‘l’aiirirw:” by l’rofcssor Kol b c. “On a new source of Acetone:” by Mr.W. Valentiri. “On some transformations of Citric Butyric and Vrtleric Acids :” by Dr. Phipson. “On the double Sulphides of Iron and Cop?er :” by Professor Pi cld. March 6th 1862. Dr. Hofmann President in the chair. The following were elected Fellows of the Society :-Thomas M. Evans Esq. 19 Queen’s-road West Begent’s- park; F. C. Matthews Jun. Esq. Driffield Yorkshire; J. D. Perrins Esq. Worcester ; Thomas Alexauder Pooley Esq. 20 Great Marlborough-street. The folioiving papers mere read :-‘‘On Specific Heat in relation to Chemical Combination iJJ by Mr. J. Croll. “ On the indifferent Hydrocarbons produced in the Deslructive Distillation of Boghead Coal :” by M. C. Greville Williams. Mr. Crace Calvert made a verbal communication upon the Actioii of Wood upon Iron.Dr. Hofmann gave an account of his experiments upon the Red Colouring Matters obtained from Aniline. March 30th 1862. Dr. Hofmnnn President in the chair. The following were elected Fellows of the Society :-Thomas Royle Esq. Crayford Kent; John Mayer Esq. Glasgow ; Leedham White Esq. Chiselhurst Kent. The following papers were read :-“On the Isolation of Phenyl ”.by Mr. A. H. Church. 492 PROCEEDINGS OF TIIE CIIEMICAL SOCIETY. ‘‘011 the production of a bluc substance by the Electrolysis of Sulpliate of Aniline ” by Dr. Lctlicb~. Anniversary JSecting March 31st 1862. Dr. Hoftnann President in the chair. The following Report was read by the President :-We have now Gentlcmen arrived at our twenty-first anniversary.The Chemical Society has come of age. Allow me as the delegate of your Council to offer my sincere congratulations on this most auspicious event. Twenty-one years ago the Chemical Society consisting then of 77 members met for the first time at the rooms of the Society of Arts; to-day we assemble a chartered body under the same roof with the Royal Society surrounded by sister societiel- with the names of 360 Fellows on our rolls. By the number of our body by the value of its contributions to science by the increasing interest which our proceedings elicit we have secured a respectable position in the world. We may look with some degree of satisfaction upon the achievements of our ycjuth and from the result of the past derive encouragement for the future.The prosperity of the Chemical Society during the past year is well marked by the slow but steady increase of the number of its Fellows and by the unintermittent flow of original contributions. The present number of Fellows as compared with the number at the last Anniversary Meeting is as follows :-Number of Fellows on March 30,1861 ............ 342 Fellows elected since that date ................ 30 , deceased.. .......................... 3 , resigned.. .......................... 1 , removed ........................... 8 Increase .................. -18 Present number of Fellows ........I ............. 360 Number of Associates on March 30 1861 .......... 10 Associates elected since that date ..................-4 Present number of Associates .................... 14 PROCEEDINGS Oh’ THE CHEMICAL SOCIETY. 403 Numbcr of Foreign Mcmhs on March 30 1861 .. . . 30 Present number of Foreign Mcnibcrs ......... . .... 30 On camparing these numbcrs with thc sttatisticsof former ycars it appears that tlie increasc in tlic number of F‘cllows duriug the last twclve months is equal to that of‘ the pr‘cccdiiig ycar aud greater tlian tlic average of formcr ycars. Tlic thee Fellows whom we have lost by dcath sitice our last anuiversary are Sir John Croft Bart. F.1L.S.; the Rev. James Cumming M.A. P.B.Y. Professor of Chemistry in tlic University of Cambridge and oiic of’the origiiial members of tlic Chemical Socicty ; and Mr.John Collis Ncshit. Sir John Croft was born iii 1778. For some ycars he fol- lowed the pursuit of‘ science especially chemistry uridcr Sir Humphry Davy. In 1818 he was elected a lklloiv of the Royal Socictp and had the honorary dcgrce of D.C.L. conferred on liim by the University of Oxford. During the Peninsular war and betwecn the ycars 1810 and 1816 hlr. Croft was attached to tlic Uritish Mission at the Court of Portugal and among other arduous duties was cniploycd by his Majesty’s minister to distributc tlie bounty voted by l’arlia-ment SlOO,OOO for the rclicf of tlic iiiliabitiliits of I’ortugal. For this and other scrviccs he received tlirough Viscourit Castelreagh the approbation of the King for his conduct during the time he was entrustcd with his Najesty’s aKairs.By the Prince ltegent of Portugal he was appointed a Knight Commander of the Royal Order of the Towr and Sword arid in 1854 was created a Baron of that kingdom under the title of Baron De Sina da Estrills. After Mr. Croft’s return to England in 1818 he was created a baronet. His early love of cliciiiistry induced him to join thc ratilrs of the Chemical Socicty soon after its formation. The Itcv. James Cuniming* was born October 24 1777. IIe entered tlie University of Cambridge in 1797 became Scllol;lr of Trinity College in 1800 and Fellow in 1803. IIe gradllatcd B.A. in 1801 obtaining honours in mathematics as tenth wrangler and proceeded to h9.A. at the usual time. While an undergraduate he seems to have spent much of liis time in the pursuit of natural philosophy arid afterwards for some I am indebted to Professor Live i ng of Camlritlgc for tllis Iliograpllical skctch.4!)4 PROCEEDINGS Om' TIlE CIIEMICAI~SOCIETY. tiiiw nscd to assist Mr. Wollastoii tlicn Professor of Natural l'liilosopliy iii tlic University in liis lcctnrcs and exupcriments. In 1S15 on tlic chtli of S~nitlisoii Tcnnaiit mlio \vas most un-fortniintcly killctl 1)y tlic fdl of a drawhridgc at noulogne hc succccclccl to tlic Clinir of Cliemistry and in 1819 ivns prcscnted to th rcctory of Sort11 Ihicton iickr Lyim wliicli had becu for-nicrly IW!C\ by Jf askclyiic th Astroiioincr Royal aid he re- taiiicd both tlicsc prcfeiiiiciits until liis clcath. IIc liwl frcqiiently in ("anihridgc ; mid thongh his licalth was ncvcr robust he coiitinnccl to givc lecturcs cvcry ycar in tlic Uiiivcrsity until the sppiiig of 1860 whcn liis coursc was iiitcrrupted by illness.This attack was folloncd by otlicrs of a niorc sevcre character and he did 011 tlic 10th Novcmbcr 1861 it his rcctory at North Riiricton having just complcted his 84th year. I-Ic rctainccl his mcrital facultics to the last ; aiid only a short timc beforc liis death hc had bcen suggestiiig experiments in physical optics. IIis pc~aoiitllnppcarmce was strikingly venerable; aid liis holiest iiiclcpcmlcnt bnt uiiostentatious cliaractcr wonfor liini tlic rcapcct of all with whom hc came in contact. He was a Pcllom of the Royal Socicty and one of the carliest promoters of tlic Cmnbridgc Pliilosopliical Society iii which body he at one timc filled tlie office of Prcaident.His natural iiicliiiatioii secrns to hsvc led him to the pursuit of those branches of physics which are coiincctcd with chemistry rather than to chcmistry propcr. Indeed in his younger days the sciences relating to heat and electricity were considcred a part of chemistry. It 11-3s tlicse scicnccs which were his favourite study and in which most of his origiiial work was done. In 1821 he communicated to the Cambridge Philosophical Society a papcr on the application of magnetism to the measure of electricity con-taining scveral new dcterminations among which may be men- tioned that of the variation due to the distance between the plates in a galvanic battery.In 1823 he communicated another' on thermo-electricity-a very remarliable paper for which he does not seem to have received due crcdit in the scientific world-in which he showed that elcctricity Eight be developcd by the un- equal heating of all kinds of conductors. He pyblished one or two other papers of a more strictly chemical character in the Transactions of the same society and also a Manual of Electro-dynamics (Cambridge 1827). In his lectures the branches of physics already mentioned had always a prominent place; and it PROCEEDINGS OF THE CHEMICAL SOCIETY. 495 was remarkable how quickly he seized the point and how clearly he expounded the bearings of new discoveries in science. In 1820 he exhibited in his lectures Oersted’s famous experiment ;and as more than one of his auditors bears witness he pointed out at the time how in these experiments might be traced the principleof an electric telegraph.His skill in manipulation was equal to the clearness of his expositions. An experiment in his hatids rarely failed; and as his Professorship was not furnished with any ap- paratus almost the whole of his physical apparatus was constructed with his own hands. To the last he kept himself au courant in matters of science ; and as soon as new processes for preparing aluminium had placed that metal within his reach in sufficient quantity he proceeded to determine its qualities in regard to electrkity. Hq made altogether very many determinations of this kind which if’ he had Eetn at all ambitious of distinction would haye been well worthy of puhlication.John Collis Nesbit was born at Bradford in 1819. He was broiight up at Manchester where his father-the author of several much esteemed mathematical school-books-conducted a large private school. The son’s attachment to chemistry was manifested very early in life and was not to be subdued by the discouragement of his friends. Having at the age of fifteen con- structed a variety of philosophical instruments including an electric battery which was purchased for 30 guineas by the Manchester Mechanics’ Institution and having afterwards delivered several lectures at that Institution his wishes were no longer thwarted and he was placed under the guidance of the celebrated Dr.D alton. When barely of age he removed to London and devoting his attention chiefly to chemistry in relation to agriculture established at Kennington his College of Chemistry and Agriculture for the instruction of youths in natural and applied science and became weil known throughout the country as a lectuier on agricultural chemistry succeeding well in illustrating his subject and in interesting his audience. Mr. Nesbi t was the author of treatises “On the Analysis of the Hop;” (‘011Peruvian Guano;” “On the History and Properties of the different varieties of Natural Guanos ;” and of a (‘Course of Lectures on Agricultural Chemistry.” He was elected a Fellow of this Society in 1845 and communicated several papers which appeared in the earliei volumes of the Society’s 496 PROCEEDINGS OF THE CIIEMICAL socIwri-.Journal. Hc was also a Fellow of the Gcological Society. He recoguised the prcsencc of phosphoric acid in the Farnham marls and contributed to thc IZxhibition of 1851 a collection of fossil phosphates which received honourable mention. In 1856 he pointed out to the Frcnch Govcrnmerit thc positions of numerous beds of coprolitcs which he had discovered in that kingdom. In 1857 he was presented by the Centd Farmers’ Club with a testimouial consisting of a service of plate arid a Ross’s micro-scope in ac1;nowledgrnent of the bciicfit R hich the agricultural community had reccived from his chemical labours and ePpecially from his successful endcavours in detecting and exposing the adulteration of manufactured and imported manures.During the latter part of his life Mr. Nesbit suffered much from failing health and died on March 30 after a lingering illness at. 42. The papers communicated to the Chemical Society and read at our meetings and the discourses delivered since our last anniver- sary are not less varied and interesting than those of former years. The contents of the papers and discourses which have nearly all appeared in our Journal being still fresh in your memory I may liniit myself here to recording their titles. List of Papers read at the Meetings of the Chemical Society from March 1861 to March 1862.:-1. ‘‘On some Derivatires from the Olefines:” by Dr. Frederick Gut hri e. 2.‘(On the Action of Dibromide of Ethylene upon Pyridine :” by T. Davidson Esq. 3. ‘(On the amount of Water displaced from the Hydrates of Eotash Soda and Baryta by Boracic and Silicic Acids :’ by Professor Bloxam. 4. (‘On the Graphite of Cast-iron :” by Professor Crace Cal- vert. 5. “On Bromide of Carbon;’ by A. E. W. Lennox Esq. 6. (( On the power ascribed to the Roots of Plapts of rejecting Poisons or other Abnormal Substances presented to them :” by Dr. Daubeny. 7. ‘(On the Constitution of Gastric Juice :” by Dr. Marcet. PROCEEDIPU’GS OF THE CHEMICAL BOCIETY. 497 8. (‘On the Action of certaip Gases upon the Peroxides of Potassium and Sodium :” by A. Vernon Karcourt Esq. 9. On some results of the Analyses of Commercial Copper <’ by I‘ Messrs.Abel and Field. 10. “On the occurrence of Bismuth in various descriptions of Copper ore :” by F. Field Esq. 11. “ On Leucic Acid and some of its Salts :” by Dr Thudi- chum. 12. (‘On the occurrence of Crystalline Depaits of Phosphate of Lime in human Urine:” by Dr. H. Bence Jones. 13. ‘I On Sparteine :” by E. J. Mills Esq. 14. “On Peppermint Camphor :” by Dr. Oppenheim. 15. ‘I On Piperic and Hydropiperic Acids :” by G. C. Foster Esq. 16. On Supplementary Experiments u$on the poyer ascribed to the Roots of Plants of rejecting Poisons aad Abnormal Sub-stances presented to them:” by Dr. Daubeny. 17. ‘‘On some Physical Properties of Tin-lead Alloys :1’ by Pro- fessor Bolley.18. ‘‘On the Dangers arising from the use of certain Waters for feeding Steam-boilers :” by Professor Bo11 e y. 19. ‘‘On the Simultaneous variation! in the amounts of Hippufic and Uric Acids excreted in healthy Human Urine:” by Dr. H. Bence Jones. 20. On the Solubility of Sulphate of Lead in Hydrochloric and Nitric Acids :” by Mr. G. F. Rod well. 21. “On a new method for effecting the substitiition of Chloriue for Hydrogen in Organic Compounds :” by Dr. H. Muller. 22. {‘On Ground Ice :” by Mr. Rkhard Adie. 23. “On Crystalline Xanthine in Human Urine:” by Dr-H. Bence Janes. 24. “ On Silica:” by Mr. A. H. Church. 25.‘‘On the Source of the Arsenic contained in Sulphuric Acid,. and on the preparation of that Acid free from Arsenic :” by professor B1oxam. 26. “On the deposit of Phosphate of Lime occurring in Teak Wood:” by Mr. F. A. Abel. 27. ‘‘ On the Composition of the Water of certain boiling springs 28. “ Note on Prbfessor Bolley’s paper on some Physical Proper- ties of the Alloys of Lead and Tin :” by Dr. Matthiessen. 29. “On the Quantitative Determination of the Alkalies in Fire- in New Zealand :” by Dr. J. Smith. clays and other Insoluble Silicates :” by Mr. G. Gore. 498 PROCEEDINGS OF THE CEEMXCAL SOCIETY. 30. ‘‘ On the Constitution and Artificial Formation of Taurine :” by Professor K o1b e. 31.“ On a new source of Acetone :,’ by Mr. W. Valentin. 32. “On some transformations of Citric Butyric aud Valeric Acids :” by Dr. Phipson. 33. “ On the double Sulphides of Iron and Copper :” by Mr. F. Field. 34. “On Specific Eleat in relation to Chemical Combination :” by Mr. J. Croll. 35. ‘I On the indifferent Hydrocarbons produced in the Destruc- tive Distillation of Boghead Coal?’by Mr. C. Gr ev ill eW i1-1‘lams. List of Discourges delivered at the Meetings of the Chemical Society :-1. “On the application of Electricity to the Explosion of Gun-powder :’ by F. A. Ah el Esq. (L 2. On the Colouring Matters obtained from Coal Tar :” by W. H. Perkin Esq. 3 ‘(On the application of the Induction-coil to Steinheil’s apparatus for Spectrum-analysis :” by Dr.H. E. Roscoe. The communications made to the Chemical Society illustrate in a measure the activity with which all the different braxiches of Chemical Science have been cultivated during the last year. To present to the Society a sketch of the progress of Chemistry during the last twelve months even were it traced in the merest outlines would be outstepping the legitimate limits of this report I must therefore be satisfied to single out of the vast number of valuable materials diffused in the periodical literature of the year a few of the researches which appear to me to claim particular attention. On the boundary line between Physics and Chemistry we meet with Magnus’ Researches on the Temperature of the Vayour of Saline Solutions which both in method and result are intimately connected with Faraclay’8 earlier investigations ; Tyndall’s experiments on the Absorption and Radiation of Heat by Gases and Vapours and on the Physical connection of Radia-tion Absorption and Conduction ; and ,D ufour’s observations on the preservation of the Liquid condition.The harvest of results in Mineral Chemistry has been particularly rich; I need only refer to the remarkable researches on Dialysis com-municated by one of our colleagues to the Royal Society which open a new page in Chemical Analysis and to the beautiful ex-periments on the influence of Pressure on Combustion which were contributcd by another. The wonderful discoveries of Bunsen and Kirchhof ham been chiefly published in thc previous year but thc fiwther elaboration of the two ncw metals Caesium and Rubidium by Bunsen belongs to the finest fruits which the last year hs ripened.The method of spectral analysis established by the resetlrclics of the two German philosophers cannot fail to exercise a powerful influence upon the direction of chemical inquiry during the ensuing decade. Already we posscss in the important dis- covery of another new element Thallium announced by one of our colleagues an additional earnest of what we may expect from the continuation of these researches. Among the important results obtairicd in the department of Inorganic Chemistry Deville’s remarkable experiments upon the reproduction of minerals must not be forgotten.The controvcrsy between Premy and Caron respecting the composition of steel has not yet been finally settled; but the interest attaclicd to the question is uncquivocally manifest from the numbcr of observers whom it has called into the field. Even more numerous have becn the labours in the domain of Organic Chemistry. The researches of Wurtz 011 Oxide of Ethylene; of Cahours on the Alcohol-radicals ; the interesting experiments of K ekul6 on Organic Acids; of S treclter on Guanine and collateral matters; of Griess on Nitrogen substitution ; the animated discussion on the constitution of Lactic Acid between Wurtz and Kolbe; the synthesis of Succinic Acid by Simpson etc.; have materially contributed to accelerate the progress of Organic Cliemist‘ry .Again I must not leave unnoticed Pasteur’s remarkable inqui- ries into the nature of fermentation although the chief results of this investigation belong to a previous period. Nor would it be right to bring this very imperfect sketch to a conclusion without alluding to the important contributions to Chemical Literature which the last year has witnessed. Dr. Miller’s excellent work on Chemistry has gone through a new edition and the chemical student has welcomed with pleasure the first parts of two long-expected books Dr. Odling’s ‘‘ Manual of Chemistry,” and Dr. Percy’s “ Metallurgy.” The unprecedented activity which prevails in the several depart- ments of Chemistry and in the collateral sciences has induced your Council to devote particular attention to the facilities of 500 PROCLaulhGS OF THE CHEMICAL ROCIETY.publication which the Society has hitherto been enabled to hold out to contributors. Duhg the first six or scvcn*years of its esistcncc tlic Clicniicnl Society publislicd the ppcrv rcad at its mectiiigs in numbcrs ap pearing at irrcgulnr intervals. The papcrs thus yublisiiccl constitute thc tlirce voluincs of rr Rlcinoirv and Yrocccdiiigs of tlic C1icitiic:il Socicty of Londoii,” 1841 to 1848. In tlie lattcr year the Menioirv aiid Procceclings n-cre rcplaccd by tlic “Qiinrtcrly Jouriial of the Cliemical Society ;” and in order to make this Journal more uscful to tlie members and acccptablc to the public it ~va9 resolved that notices of all important papers upon Cheiiiical subjects published in foreign journals should be appended to cadi nnmber ; and fiirtlier that tlie January number of each year should contain an alplinbetical list of the heads of all chemical papers published during the year both at home and abroad np to the time of tlie publication of the Journal.In strict accordance with tliesc resolutions the Quarterly Journal of tlie Chemical Society was publislied up to the year 1860 when it was found.coiivenieiit to discontinue the aIphalietica1 list of the lieads of Chemical papers. In fact this list which mlicii first published occupied not more tliari niiieteeri or twenty pages had gradually espanded bcyond legitinlate proportions filling in the last 11urnc in which it appcared riot less tlian 79 pages or one-quarter of the whole volume.By its discontinuance a considerable amount of additional spacc was thus given for origiiial communica- tions and for abstracts but it proved inadequate to the requirements of the Society. In 1860 and 1861the improvement of the Journal had been repeatedly under the consideration of the Council ; who ultimately deeidcd that the Quarterly Journal should be replaced hy a Monthly Journal each number to contain two and a-half sheets whereby the annual volume mill be raised from twenty-four to thirty sheets. The rank a society holds will always depend upon the number value and rapidity of its publications I believe therciore that the transition from a quarterly to a monthly journal will be received nith general approbation.Not only does this change secure to our contributors almost immediate publication but it will enable 11s also h‘enceforth to publish abstracts of all valuable chemical papers wliich are dispersed in the Proceedings and Transactions of tlie several learned socicties in which they are riot always easily accessible and to make our journal a sort of Compte iiendu of all the work done in chemical science throughout the country. I now call upon you gcntlemen to proceed to ballot for tlie PROCEEDINGS OF THE CHEMICAL SOCIETY. oficers of thc ensuing year. The Secretary will then read sotnc of tlic Bye-laws whicli havc been rcvisetl by your Council various altcratious having suggested tliemselrcs by tlic cs1)crieiice of the ten years which have elapsed since tlie Bye-laws were last under your consitleration in 1852.Priritcd copies of the revisul Bye-laws are upon the table; I trust thikt tlie altcrationu will mect with your approval and receive your sanction. The meeting then proceeded to elect the Council and Officers for thc ‘ensuing year and the following were declared to have been duly elected :-President.-A. ISr.Hofmann Ph.D. L.L.D. F.R.S. Vice-Presidents who hwv? Jilled the @ce of President.--W.’1‘. Brandc F.R.S. B. C. Brodie F. It. S. C. G. B. Daubeny, M.D. F.R.S. Thomas Graham F.R.S. W. A. Miller N.D. F.R.S. Lyon Playfair C.B. F.R.S. Col. Philip Yorke F.R.S. Vice-Presidents.-H. l3en c e J on cs 31.D. F.R.S . A1f r ed Smce F.R.S. -4.W. Williamson F.R.S. Eobcrt CVar-ington. Secretaries.-1’. Redwood Ph.D. 11‘. Odling M.B. F.R.S. Foreign Secretary.-E. Frankland Ph.D. F.R.S. Treasurer.-Warren De la Rue Ph.D. F.R.S. Other Members of Council.-F. A. Abel F.R.S. Thomas Andrews M.D. F.R.S. William Francis Yh.D. F.L.S. J. H. Gladstone Ph.D. F.R.S. J. 13. Lawcs,-F.R.S. G. H. Maltins A. Matthiessen Ph.D. F:R.S. A. Normandy, W. H. Perkin H. 2.Itoscoe Ph.D, Edward Schunk Ph.D. F.R.S. John Stenhouse L,L.D. F.R.S. Some alterations in the Bye-laws duly sanctioned by thf Council having been submitted to the meeting It was moved by Dr. Odling seconded by Mr. Warington and resolved- ‘‘ That the existing Bye-laws be abrogated and annulled and that the following be the Bye-laws of the Chemical Society ”-[These Bye-laws are published separately.] It was moved by Professor Faraday seconded by Mr.Makins and resolved- “That the thanks of the meeting be given to the President and Council for the services rendered to the Society during the past year.” Das. THE TREASURER IN ACCOUNT WITII TIIE CIIBMICAL SOCIETY OF LOKDON CR9. 1861. s. ti. 1861. af 8. t!. di d. 3. March 25. Po Cash in hand .,......................... . . ....................... 569 11 10 Joiiri~al. By Editor’s Pnlnrp to 95th hlar$ 1862 ............... 80 0 0 1862. Printing Journnl .......................................... 002 19 11 March 11. Half-yearly Dividend on &.500 3 per cent. Console ..... 745 1)istiibuting Journal ........................ ............7 16 0 J on &600 -290 5 11 ::Sundv Receipttfrom March 25th b61Jto M&ch i5;i 813 3 Library. Lihrarinn’s Salary to 25th hlnrch 1862 ............ 05 0 0 1862 as below :-Proceeding* of tlic Royal Society .................... 50 0 0 d. s. d. Books and Magazines ..........................,......... 27 0 0 Life Compositions ........................... 59 0 0 Bookbiuding ..........................................,..... 8 18 2 Admission Fees .............................. 64 0 0 110 18 2 Resident Members’ Subscriptions pre- Collector Collector’s Commiasion .,............................... 29 16 0 .............. 10 0 0 and Clerk. Clerk ......:..................................................I -S 0 0 __ vious to 1861...............# Non-rerident Members’ Subscriptions I16 0 previous to 1861 ........................4 0 0 Gt at ioiierr Account Rook Poatnge Envelopes Receipt Resident Members’ Subscriptions for ’ostage &* Sttmps &c. ........................................... 61 1 1861 ....................................... 78 0 0 Draft Stamps ..............,.. . ........................... 0 4 0 1 Kon-resident Members’ Subarriptions Carriage of Bnoks Stationen, gtc. .................. I 18 for 1861 .................................... 23 0 0 Engrossing Ad~lremto Her Llnjesty ............... 05 0 Resident Members’ Subscriptions for 96 1862 ....................................... 972 0 0 TToii3e Royal Society Share of Expenses for Refresli- Non-Resident Members’ Subecriptions Expenses.ments .................................._. ... ......... .. . . . . 1; 18 for 1862 .........,.......................... 92 0 0 Thos. Hux Salnry to 05th Marcli 1863 ............ 80 0 696 0 C , (as per book) Gas Oil &r. ........ ... 114 JJ Glazing Painting &c. 1s W.&e Cleaning ...................................... 11 Gate Porter Christmas Gratuity ..................... 11 -40 19 3 Furniture. Balloting Boxes (R. Irelnnd).......................... 10 lo 0 -10 10 0 Purchase of dl00 3 per cent. Consols .,...,.,....... 90 0 (J --90 0 0 June 13. Balance at Messrs. butts and Co. .................. 556 17 8 ) in Cash in hands of Treasurer ............ 41 0 0 -597 17 8 --I_ d 1181 9 f E 1181 96 Assms. C a. cl. Cxamined aud found correct PHILIP J.CHAROT. ....... 597 17 8 GEORGE GLL4DSTONE, Balance in Cwh ............................................ Inverted in 3 per cent. Consols .................... .......... 600 0 0 W. H. THORNTHWAITE, - 81197 17 8 PROCEEDINGS OP THE CHEMICAL 8OCIETY. 503 April 3rd 1862. Dr. IIofmann ‘President in the chair. The following were elected Fellows of the Society :-A1 fr ed S id e b ottom Esq. CToomn-street Wyndham-road Camberwell; C‘. Haughtou Gill Esq. 52 Chancery-lane ; William Symons Esq. 17 St. Mark’s-crescent Regent’s-park. Dr. Debus delivered a discourse-<‘On the Influence of the Quantitative Method on the Development of Scientific Chemistry.” April lTth 1862 Dr. Hofmann President in the chair.The following were elected Fellow of the Society :-Dr. Julian Courtauld Braintree Essex; Dr. C. M. von Bos6. The following paper was read :-‘‘ On the Action of Carbonate of Ammonium on Magnesian Salts:” hy Dr. Edward Divers. May lst 1862. Dr. Hofmann President in the chair. The following were elected Fellows of the Society :-Peter Spence Esq. Pendlston Alum Works Manchester ; Charles Graham Esq. Berwick-upon-Tweed ; H. G. Madon B.A. Queen’s College Oxford ;W. Es s on B.A. Merton College Oxford. Dr. Thomas Anderson delivered a discourse-rc On t!ie the Chemistry of Opium.” May 15th 1862. Dr. Hofmann President in the chair. M. H. St. Claire Deville delivered a discourse-“ On Vapour-densities.” 604 PBOCEEDINOS OF THE CHEMICAL SOCIETY.&fay 29th 1862. Thomas Graham Esq.,Vice-president in thc chair. The following papers were read :-‘(Ou the Action of Mordants upon Cotton-fibre :” by Walter Crum F.R.S. “On the Capacity of Arsenious Acid for Bases and on certain Arsknites :” by Professor Bloxam. Additional notea-“ On Reciprocal Decomposition among Salts in Solution :” by Dr. Gladstone F.R.S. “On the General Occurrence of Titanic Acid in Clays:” by Mr. E. Riley. June 5th 1862. Dr. Hofmann President in the chair. The followiug were elected Fellows of the Society :-Charles Low Junr. Esq. 3 St. James’s-road Holloway ; Fern side Hudson Esq. Laboratory Corporation-street Man- Chester. Professor W ur t L delivered a discourse-(‘On Oxide of Ethylene considered as a link between Mineral and Organic Chemistry.” June 19th 1862.Walter Crum Esq. in the chair. Messrs. Cannizzaro Kekul6 Loew ig Ma1 aguti Marig- nac Pasteur Stas and Zinin were elected Foreign Members of the Society. Dr. Marcet delivered a discourse-“ On the Chemistry of Digestion.” The following papers mere read :-‘‘On Berberine contributions to its history and revision of its formula:” by Mr. W. D. Perrins. “On the Formation of Iodides of the Alcohol-radicles from Boghead Naphtha:” by Mr C. Greville Williams F.R.S. PROCEEDINOS OF TXE CHEMICAL SOCIETY. 605 November 6th 1862. Dr. H of m an n President in the chair. 1’.A. Bowman Esq. of‘Halfax was elected a Fellow of the Society. The following papers were read :-“ On the Separation of Tin from Antimony and on the Ana-lysis of Alloys containing Lead Tin Antimony and Copper :Ir by Charles Tookey F.C.S.“On a Volumetric Process for the Analysis of Water :” by E.N ic holson F.C.S. A note from Professor Heintz to Dr. H. Bence Jones- ‘< On the Composition of the Amorphous Ueposit in Healthy Urine,” was next read. rc On Hypobromous Acid :” by William Dancer. November 20th 1862. Dr. Hofmann President in the chair. W G. Blagden Eeq. was elected a Fellow of the Society. The following papers were read :-(‘On the Forniation of Organo-metallic Radicles by Substitu-tion:” by Q. U.Buckton Esq. “On the Specific Gravity of Urine ap a measure of its solid Constituents :’j by E. Nicholson Esq. Dr.H of m an n demonstrated the Properties of the Sponta-ncously Inflammable Silicated Hydrogen Gas discovered some time back by Buff and Wohler December 4th 1862. Dr. Hofmann President in the chair The following were elected Fellows of the Society :-= George Farrer Rodwell Esq. 15 Great Marlborough-Rtreet ; G. W. Septimus Piesse. %a. 2 New Bond-street; Thomas 606 PROCEEDINGS OF TIIE CII I‘hI ICAJA SOCIETY. Farmar Hall Esq. Kennington ; William Gossage Esq. Widness near Warrington; John Chapman Wilson Esq. Making Place Hall near Halifax; James Richards Esq. Clifton Lodge near Preston,,Lancashire ; Magnus If. Tait Esq.; W. H. Michael Esq. M.R.C.S. Northwich Harrow. John Henry Baldock Esq. 55 St. James’s road Holloivay was elected an Associate of the Society.The folIowing papers mere read :-“Notes on cerlain Processes of Rock-formation :” by Mr. Arthur’ H. Church. “On the Determination of the amount of Organic Matter in Drinking Water by means of a Standard Solution of Permanganate of Potash :” by Dr. Woods. ‘‘On the effect of Heating Sulphate and Sulphide of Lead in Hydrogen and Carbonic Oxide ’’ by Mr. G. F. Rodwell. “On the Composition of Gall-stoDes ’’ by Dr. Thudichum. December 18 1862. Dr. Hofmann President in the Chair. Messrs. W. A Dixon John Hooker Alexander Taylor Machattie and Edmund James Mills were elected Fellows. Dr. Frankland gave an account of some experiments made by Messrs. .Wanklyn and Erlenmeyer on Hexylic Alcohol. Mr. Fie1 d read a note-“ On the Solvent Power exercised by a Solution of Hyposulphite of Soda upon many Salts insoluble in Water.” Donations to the library received in the year 1862 :-“On the Physical Forces concerned in the Phenomena of Vegetation :” by C.Daubeny M.D. F.R.S. from the Author “On the Concrete used in the late Extension of the London Docks;’’ by George Robertson C.E. from the Author. ‘‘ Vis inertia uicta or Fallacies affecting Science :” by James Reddie from the Author. “Researches on the Solar Spectrum and the Spectra of the Chemical Elements :” by G. Kirchhof trarislatcd by H. E. Ros-coe from the Translator. “Cheinical Coiitributions to Silliman’s Journal :” by M. Caroy Lett from the Author. “Notes on tlie Cliiiicse Matwia lllledicri :” by Danic 1 Iitan-bury from the hntlwr.“ On the Sonrccs of the Nitrogcn of Vcgctatiori :” hy J. B. Lawes J. 13. Gilbcrt aid Evan Pug11 from the Authors. ‘‘Fifth Report on Experiments on thc lkditig of Sheep :” by J. B. Lawes arid J. €1. Gilbert from the Authors. ‘‘Tho Sulphimous Bath at Ssiidefiord in Norway :” by Drs. Ebbesen and Hiirbye from the Authors. “Tlie Chemistry of Soils :” by Dr. Scoffern from the Author “ Gold-mining and the Gold Discoyeries made since 1851 :” by J. A. Phillips from the Author. ‘‘Contents of the Correspondence of Scientific Men of the Seventeenth Century:” by Augustus De Morgan from the Author . ‘‘A nnsthcsia considered espccially in reference to operations in 1)cntal Surgery;” by A. Coleman from the Author.“On a Series of Organic Compounds containing Boron :” by Dr. E. Prankland from tlie Author. “A Dictionary of Calico-printing and Dyeing :” by Charles O’Neill from the Author. nesults of the Meteorological Observations made- under the direction of the Unitecl States’ Paterrt Office and the Smithsonian ?nstitution from 185%to 1859 inclusive being a Report of the Commissioner of Patents made at the first session of the 36th Cuiigrcss Vol. I :” from the Srnithsonian Iristitution at Wash-ingto:i. 1‘ Sinithsonian Miscellaneous Collections,” Vols. I to IV from the Sniitlisonian Institution. ‘(Report of the Commissioner of Patcnts (U.S.) for the year 1861:” from the Agricultural Commissioner. ‘‘Circular from the Commissioner of Agriculture (U.S.) on the present Agricultural Mineral and Manufacturing Con-dition and Resources of the United States :” from the Commis- sioner.On the rolling and Casting of Metals :” by J. Tylor EsqP from the Author. 60s PROCEEDIXGS OF THE CHEMICAL SOCIETY. ‘‘Statistical notes of the progress of Victoria from the founcta-tion of the Colony :’7 First series Parts 1 2 (1835-18GO) by W. €1. Archer ‘< Statistical Register of Victoria from the foiindation of the Colony with an Astrononiic:il Calendar for 1855 :” edited by W. €I. Archer. ‘‘The Victorian Gcvernmcnt Prize Essays :” (1860.) I‘ Catalogue of the Victorian Esliihitioii of 1861 with Prefatory Essays;” by W. H. Archer aid others. The Catalogue of the Melbourne Public Library ” for 1861.“Essais divers servant d’introduction au Catalogue de 1’Espoai-tion dea Produits de la Colonie de Victoria par W. H. Archer &c. Die Colonie Victoria in Austi*alien ihr Fortsckritt ihre H iilf squellen und ihr physilialisclier Charakter in Abhand-lungen yon W. H. Archer from the Council of the University of Melbourne. (‘Dictionnaire dc Chirnie Industriellc ;” par MM. Barreswil et Girard Totne IT Pt. 1 from the Authors. “Estujlios quimicos sobre el Aire Atmosferico de Madrid ;” yor D. Ramon de Luna from tlie Autlror. Lecciones Elementares rle Quimica G6nera1,” Tomos I I1; por Don R. Torres MUEOZde Luria from the Author. “Zum Gedachtniss an Jean Baptiste Biot (gesprochen in der iiffentlichen Sitzurig der konig1.-bayer.Akademie der Wissen- schaften am 28 Marz 1862):7’ von Carl. F. Ph. von Martius. “Denkrede auf Gottliilf Eleinrich v. Ycliubert:” von Dr. Andreas Wagner from the Royal Bavarian Academy of Sciences. Periodicals :-‘‘ Philosophical Transactions,” 1860 Pt. 11 ; 1861,Pts. I 11 IT and 1862,Pt.I. List of Officers and Fellows of the Royal Society” (1861) from the Royal Society “Transactions of the Royal Society of Edinburgh,” Voi. XXII Pt. 3 (Session 1860-61) and Vol. XXITI 13. I (Session 1861-62.) ‘(Procceditigs of the Royal Society of Edinburgh,” 1860-61 and 1861-62 from the Royal Society of Edinburgh. “Memoirs of the Ropl Astroiiomical Society,” Vol. XXX. “Monthly Notices of the Proceedings of the Royal Astronomical PUOCEI$DINOS Ol” ‘I’tIE CIIEMICAL BOCIETY.509 Yociety,” from December 1SG1 to Decembcr 1862 from the Society. ‘(Quartcrly Journat of thc Gcologicd Socicty,” for 1862. (‘Atldrew ‘dclivered at the Anniversary Meeting of the Geolo- gical Society,” February 21 1862 ; hy I’rofessor Iiuxley from the Gcc,logical Society. “ Jouruai of the Pliotographic Societ!,” for 1862 from the Society. ‘‘ Pliar~riaccriticalJournal,” for 1862 from thc Editor. “Journal of the Society of Arts,” No. 473-525 ; from tho Society. ‘‘ Chemical News,” KO.151-158 from the Editor. .‘Lmdon Review,’’ No. 74-128 from the Editor. Literary Gazette,” No. 177-198 from the Editor. The Partlienon,” No. 1-33 from the Editor 6‘Cdendar for the year 1862 of tire Science and Art Depart- meiit of the Cornmittce of Council on Educatioii :” from the Department.“ The Loiidon Mzdical Review,” February 1862 from the Editor. “ Mining arid Smeltiiig Magaziiic,” for 1802 from the Editor. (‘PvIcruoirs of thc Literary and Philosophical Society of Man-Chester,” Vol. I 3rd Series. “Proceeding? of the aame,” Vol. 11 Sessions 1860-61 and I 86 I 42. ‘(Etules of the same ” (1861) from the Society. (‘Proceedirlgs of the Literary and Philosopmica1 Society of Liverpool,” i861-62 from the Society. “Caiisdian Naturalist and Geologist,” from December 1861. to October 1862 ; from the Natural History Sociexfof Montreal. Canadian Journal,” March 1862 from the Canadian Institute ‘‘ Repertory of Patent Inventions ” (eiilarged series) No. ‘787 -816 tiom Measrs.De la Rue and Co. (( ‘Srnithsonian Report,” for 1860 from the Smithsonian In-etitntion at Washington. “American Journal of Science and Arts,” for 1862 from the Editor. ((Journalof the Frauklin Institute,” for 1862 from the Institute. ‘‘Proceedings of the Academy of Natural Sciences at Phila-delphia,” 1861 from the Society. 510 L’HOCl3EDINGS OF TIIN CIIEMICAL BOCIE’I‘Y ‘‘l’rocccclings of thc Amcrican Philosophical Society,” for 1861- from tlic Socicty. ‘‘J3ullctin (l( la SociW d’l~ncouragcmcnt pour 1’Industric Natio\i:ile.” No. IOG-IOS from thc Socicty. “niilletin dc l’Acnd6rnic 1ml)drislc clcs Scicriccs dc St. l’cters- bonrg,” Toinc IV from tlic Acfitlemy. ‘‘Mdlmgcs t’liysiqiics ct Cliimiqueu,” tires du Bulletin de 1’Acadhic Iriipclrialc des Scicnccs dc St.Pctershourg Tome IV. Livr. 1-6; Tomc V. Liv. 1 from Profcssor Fritzscirc. “Bullctin des SCances de la Clasae des Sciences c\e 1’AcadBmie Itoyale dc Yelgique ” (1861). “Annusire de l’hcadbmie Ropale de Belgique” (1861) from the hcatlcmy ‘‘Mcinorias dc la Rcal Acadcmia dc Ciencias de Madrid,” Tomos 3 4 5. “Rcsurncn cle las Actes de l’hcrrdemih de Ciencias dc Madrid,” 1857-1860. ‘‘Programas de Premios,” 18GO-G2 from the Academy “Mcmoric clcll’ Accademia dellc Scienze dell’ Istitrito di Bologtia,” Toino X lhsc. 2 3 4 c Torno XI froin tlic Academy. “ltcndicoiiti ilcllct Sessioni dcll’ Accsdcmis dcllc Scicnzo deli’ Istituto di Bologna,” 1859-60 and 186041:from the Academy. ‘‘Denkscliiften der Kaiscrlichen Akadeniie dcr Wisseuschaften in Wien (math-phys.Classc),” Band XX. ‘‘ Sitzungsberich te derselben (math-phys. Classe) ,” Bde. XLIII XLZV aid Bd. XXV lte Ahtli. ITcfte 1-2; 2te Abth. 1 2 3. “ Register dcr SitzuiiSsberichte,” Bde. 3142 from ttic Impcrial Acadcmy of Sciences at Vienna. ‘I Abhandlnngen dcr kiiniglich-b,?ycrischen Akademie der Wis- wnschaften in Muiichen,” Bde. I-IV uricl Bd. IX 2te Abtheilung ‘‘ Sitzungsberichte derselben,” 1861. Bde I 11 and 1862. 13d I Hcftc 1 2,3. ‘(ltccle in der offentlichen Sitzung derselben,” am 28 Nov. 1861 von J. v. Liebig. I‘ Vcrzcichniss dcr Mitgliedcr dcrselben,” 1862 from the ltoyal Bavarian Academy of Sciences. ‘‘Zeitsclirift fur Chemie and Pharmacie,” herausgegeben von Dr.E. Erlenmeyer 1862 from the Editor. ‘‘ Jahrbuch der k. k. Central-Anstalt fir Meteorologic and Erdmagnetiemus,” voii Karl Kreill Bd. VIII Jaiirgang 1856. ..*ROCEEDINGS OF THE CHEMICAL socmw. 511 ‘‘Jahrbuch der k. k. gcologischen Reichsztnstalt zu Wicn ” XI Jalirgang 1860 from the Institute. ‘Terhandlungen der naturforsclicnilcn Ccsellschaft in Bascl.” Diitter Theil. Ihfte l,’2 3 from the Society. 0fvcrsigt af Kongl. Vetenskaps Akacle 111iens ForhahtlIi n gar,” 1860-1861 from the Royal Academy of Sciences at Stockliolm. “Abhanclluxigen der naturwissentschaftlichen und tcchriischcn Commission der bo1iigl.-bnyr. Akadcmie der Wissenschuftcn :” from the Royal Bavarian Academy of Scicnccs.

ISSN:0368-1769    

DOI:10.1039/JS8621500489

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

INDEX. A. Abel F. A. on tho cxintcnw of con. eiderable dcpoeitu of crystalliscd phos-phate of lime in tcnk wood 91. Acetate of ctliyl capillary transpiration of of 439. potash diffudon of in alcohol 228. of eycoceryl 67. Acetone capillary transpiration of 440. Acid acetic capillary tranapiration of 433. -compo~itionof aqueous of constant boiling point 273. -acetic determination of its vnpour- density 163. Acid anthracenic 49. -arsenious 889 arsenioue mid. -butyric capillary transpiration of 434. butjric transformatione of 141.-carbonic determination of in iron ores 337. -carbonic on the properties of liquid by George Gore 163. -chlorethylsulphuric 96. -chloreth,ylsulphuric conversion of info tnurine 101. -citric transformations of 141.-formic capillary transpiration of dab. formic composition of aqueous of constant boiling point 371. -hydropiperic analysis of 20; -insolinic conversion of the cymole from turpentine and caoutchin into 121. bemipinic 453.-bippuric on the simultaneous variaL tions of and of uric acid in healthy urine 81. -hydriodic; its action on erythro-mannite 461. -hydriodic it9 action on melampy-rine 468. -hydrochloric it6 action on cyanide of ethylene 137. -hydrochloric ibaction on melam. pyrin 458. icid hydrochloric cnpillnry ti*arispir&-tion of 430. -hydrochloric its com1)iiiatiuri wilh pci’l’crmint-camphor 28. -bgdrochloric diffusion of 227. -Iiydtochloric soluLility of sulphato of lcad in 59. -hypobrornous on by W.Ilanccr, 477. -meconic 450. -mct.irrtnnnic and dialysis of 255. -nitric its action on nntbraccnc 48. -its adion on cyanido of etlijlcr~o, 137. -riitric it8 action on qcoretin 66. -nitric capillury transpiration of, 431. -nitric and nitrourc on a mcthoct of dctcrmining; by A. Vernon Har-court 381. -nitrk soluhility of sulphatc of lead in 59. -nitric its vapour density 154. 0-o iilnic 453. -ptosphoric determination of in iron ores 337. -piperic analpis of 18. -pyr tartaric its formation from cyanide of propylene 139. -. pyrotartaric on the ijpthesiu of by Maxwell Simpson 134. -silicic 80luble; preparation by dia. lyeis 244. -eolventa action of. and reciprocal decomposition in alcohol,‘ 307.-succinic ;its formation by the ac-tion of pottish on cyanidc of etljlene, 136. -auccinic on the sptheeia of by Maxwell Simpson 134, -euceinic on the transformations o citric butyric and valerianic acids with reference to the artificial pro-duction of by T. L. Phipeon 141. -eulphuric its action on caoutchin 122. -eulphuric ite action on Bycoretin, 66. -sulphuric capillary transpiration of 432. 514 1NDEX. Acid sulphutic on the presence of arsenic in commercial aud on the prepara- tion of that acid free from arseuic by C. L. Bloxam 52. 7eulphuric volumetric estimation of in wntere 474. -titanic Bee titanic acid. -uric on the simultaneoue variations of,and of hippuric acid in healthy urine 81. -valerianic capillary tranapiration of 434.7valerianic transfomatione of 141. Acide caplllary transpiration of 440. -on the compoaition of aqneoue of conatapt boiling point by H. E. Roecoe 270. Adie R. on ground ice 88. Albumin dial+ of,260. -ditFueion of 224. Alcohol copillary traaepiration of at 20" c 437. J -(apillq-trampintion ot at differ-ent temperatures 444. -determination of Itr vapoordedty, 146 146,162. -Won of iodine and acetate of potaah in 228. -diffusion of solution of reein In,228. -reciprocal decomyosition in 307. -benzylic on a new homolope of by Warren De la Ria and Hugo MUller 62. -hexyUc 461. -mentholic 29. -eycocerylic action of chloride of phosphomae on 78. -eycocerylia pmpantion and corn-poeition of 71.-radiclea on the formation of the iodide0 of the fmm bogherd naphtha by C.Or.Willisma 369. -rsdicles un the hydridea of the existing in the products of the db tillation of carinel coal by C. Bchor-lemmer 419. Alcohole apilluy trsnsfomtion 04 439. Alkalies on the determination ot in fire clay and fire-bricb by O.Gore 104. -determination of in iron owe 338. -volumetric estimation of in watera 473. and alkaline earthe action of bm mine on the queoue eolutione of 476. Alloye containing lead tin antimony and copper on the analyah of; by C. Tookey 462. -of tin and lead on Home pbpsical propertiea of by Profemor Bol ley 30. -BemluLa thereon by A. M at t hie e-@en,106. Alumina eoluble preparation by dlaly-eis 217.-and sesquioxide of iron eeparation of by potash 331. -and titanic acid experiments with 325. -titanic acid and Boaqhioxide of iron separation of 333. Alvins cvacustion object of 418. Ammonia aqucoue ite vapour-density, -atsenite of 297. -and titanic acid experiments with 327. -boric &hide 369. -boric methide 377. Ammonium pn the action of carbonate of on magncsian ealta:by E. Dive re 196. -hydropiperata of 21. -and magnesium carhnate of 199. Amorphoue sediment in urino ita de-compeition by waehing with water 206. Amyl bydride of from cannel coal 421. -iodide of from boghead naphtha, a Amylamine platinum-mlt of 561. Amylic alcohol capillary tmnaformation of 439.Analyeie on liquid diffudon applied to ; by 9'. Graham 216. -of watem on a volumetric pmcea for the by E.Nicholeon 477. Anderson Thomae on the chemistry of opium 446. Andereon T.,on the conetitation of anthrscene or paranaphthalin and on mme of the producta of its decompo-eition 44. Anhydride hypobromone attemptr M preparo 486. Aniline on the production of o blue eubutance by the electrolysis of 0Ul-pbte of by H.Letheby 161. Animal mucue dialysia through 242. Annivmry Meeting of the Chemical tkiety (Mmh 30 1862). Anthracene action of bromine on 49. -action of chlorine on 61. -action of nitric acid on 46. -bichloride of 61. -on the conatitntion of by T.An-d ereon 44. -hexbromide of 49. -tetrabrominated 60.Anthracenuee 46. Antimony lead tin and copper,anrlysie of alloye containing 462. -on the eeparation of from tin;by C.Tookey 462. Amenic on tbe preeence of in the eulphuric acid of commerce and on the INDEX prcparation of that acid frcc from ar senic by C. L. Bloxham 52. Arscnioun acid its action on the car-b0nate.r of potaesa and soda at 212" F. 281. -acid on the capacity of for bases oncertaiuarscnitcs byC. L. Bloxam 281. -acid scparation of from colloidal liquid. 261. Ar.-clritc of ammonia 297. -of hry ta 29 4. -of copper 298. -of magnesia 204. -of silvcr 290. I_ of zinc 29F. .iracnitcu on ccrtain:'by C. L. Bloxam 231. ;Iroenites of lead 291. -table of the composition of 298. Atmospheric yresure its influence on the rate of combuetion 170.-prcasiire on tlic influence .of on some of the phenomena of combustion by 1:.Frankland l€8. -preesure its influence on the light of combustion 177. Atomic Weights of elements 390. B. I3alnnce ahcet of the Chemical Socicty 1862. Baryta arsenitc of 294. Barium hydropiperate of 23. -piperate of 18. Baryta-water action of bromine on 479. -boric mcthide 380. Bases oxycthylenic 405. Benzoate of uycoccryl 74. Bcnzylic alcoliol on a new homoloque of:byWarrcn De la Riieand Hugo Miillcr 62. Berbcrine biohromate of 348. -chloroaurate of 345. -. chloroplatinate of 344. -contributiuns to its history and revision of its formula by J. D. Pcrrina 439. -hydriodate of 351.-hydrobroniatc of 350. -. nitrate of 349. -teriodide of 352. -usesof 356. -and silver hyposulphite of 347. Bichloride of anthracenc 51. 'Uichromate of Liherine 349. Bile its power of emulsioning fatty acids 416. Biniobcrbcrine hydriodate of 352. Biuitroxanthracenc 49. Bkst-furnace cinder (slag) composition of 314. Bloxam C. L. on the capacity of aracnioue acid for bases and on cer-tain araenitee 281. -. on the EOUI'CC of the arecnic in the EUlphilriC acid of commerce and the prepnrcitim of that acid free from arwnic 53. Boghcad cod see coal. -n:iphtha on the formation of the iodiclea of the alcohol-radicle8 from by C. Ctr. William~ 359. Bolley l'rofeamr ncw experiments on the dangers arising from the une of certain waterd for feeding steam-boilers 32.-on some physical properties of the alloys of tin and lead 30. Boiling sprinq note on the composition of a. in Kew Zealand by Profeasor Smith 57. Borate of ctlivl. action of zinc-dhsl 367. -of cthyi 'action of zinc-meihyl on 3i5. Boric dioxycthidc SiO. -cthide 367 -mcthide 373. -methide its compcunds with potaeh soda lime and bavta 379. Boron on a new sex$ of organic com- pounds containing by E. Fr an klan d 363. Bricks fire determination of silica and titanic acid in 314. Bromine i_tR action on anthracene 49. -its action on ieoprae 138. -its action on peppermintcamphor 29. -its action on dry oxide of mercury. 483. -its aolubility in water 487.-water its action on oiide of men cury 481. -its action on aqueoiia solutions of the alkaliesand alkaline earths 476. -its action on solutiou of nitrate of silver 479. -comparnt ve experiments on the action of on caoi:t&in and oil of tur- pentine 117. Bulb dialsser 239. Butyrate bf ethyl capillary transpiration of 439. Butyrate of methyl 27. C. Calcium hydropiperate of 22. Camphor of peppermint on the by A. Oppenheim 24. 516 ISDEX. Candler oamburtlon d:indoonce of at moe beric preseure on ita rate 170. Csnnef coal t3ee Coal. Csoutchin action of rulphurlo wid OD 122. -oompoeition of 116. -its oonvereion into cymole and para-cymole 119. -and iaoprene,'on by C. Or.W i1-liarne 110. -tableof tbeir phyeiaal properties 123. -their polymerio relations 117. -end oil of tu ntine comparative axpcriments on X wtion of bromine on 1.17. Caoutchouc compoa:tion of 122. -on the relat on of the Hrat and eecond liydrocarbons produced by ita dietillation 116. Caproyl hydride of from camel owl 422. -from canocl coal 425. -iodide of &om boghead naphtha 861. Caprylsmine platlnum-ealt of 361. Caramel dialjeia of 258. -diffueion of 224. Carbonate of ammonia on the action of on magnesia dts by E. Divers 196. -of magnesium and ammonium 199. Carbonates of potama and soda action of ardenious acid on at 212" B. 281. -.at a low red heat 287. -of potsesium and odium action of bromine on eolutioos of the 476.Chemical Society anniversary meeting (March 30 18S2) 492. -balance heet (1862) 602. -donatione to the library (1 862) 606. 9-proceedin@ at the meetinge 489, -report of the yreeidcnt and council 492. Chemistry of digeation on the by W. Marcet 407--of opium on the by T. Ander-eon 446. -organic and mineral on orido of ethjlcne considcred as 8 link between by A. Wurtz 387. Chloranthracene 61. Chloride of chlorethylsulphuric acid 96. -of mentligl 27. -of phoephorus it8 action on syco-cerjlic alcohol 13. -of otassium diffueion of a mixture of anasulphate of eoda 234. Chloride8 of potaaeium and sodium dif- fusion of a mixture of 230. Chloride of eodiurn action of bromine-water on 478. -ita diffueion 222 215 227 230 231 232 234 236.Chlorlde of sodlam mixtum of with tbe mlpbabpf sodr and potaoh 281, 288 ~ 4 , -of eparteine 8. -of zinc and rpsrieelne 4. Chlorine note on a mothod of effectlng the eubetitutfon of for bydiogen iir organioconipounde by Hugo MUller 41. -volumetric mtimatlon of in wateru 474 Chromic. oxide eoluble dialyris of 254. Church A. H. obeervatione on eilica 107. Cinder bht furnace (alag) comporitlon of 314 Circolar polarhation mcthod of quanti-tative determination by 308. Clay blue from Wiltshire analysis of : 23. Claye on the general occurrence of tttanio acid in &c. ; by E.Riley 311. Coal canncl on the hydrides of tho alco-hol-radicle8 exieting in the products of the distinctive distillation of by C.8chorlernmer 419. Coal on the hjdrocarbons produced by the deetructjve distillation of Bog. head by C.Or. William~ 130. Codeine 450. Colloldul condition of matter 265. -liquids ; eeparation of arseniour acids from 261. -eubetances ; their preparation by didyeis 243. Colloid fubstancee organic dialyses 0s 25s. Collo'fdq 217. Combuetion on the intlueuce of atmoe-ph0r.c preeeure on some of tho pheno- mena of by E. Frankland 168. -iufluence of compreaeion of the air on the light of 187. -influence of mtefiiction on the light of 177 CombustIon of candlea influence of at moepheric preaeure on ite rate 173. -of time-fueee iufluence of atmoe-pheric preasure on ik rate 170. Comprewion of the air; its influence on the light of combustion 187.Copper smenite of 292. -dialysis of ferrocyanide of 253. -dialybis of eucrate of 253. Copper and iron onfhe douhle aulphidee of by F.Field 126. Copper iron and potsaeium on a corn-plex cyanide of by W. Wonfor 357. Copper lead tin and antimony anslyah of alloys containing 462. Cotamnine 452. INDEX. 617 Crystsllised phosphate of lime on the occurrence of deposits of in human urine by H. Bence Jones 8. Crystallo'ide 2i7. Cyanide on a complex of iron copper and potassium by W. J. Won for 357. Cyanide of ethylene action of nitrate of ailver on 137. -acticn of potash on 136. -its preparation 135. -action of nitric and hydrochloric acids on 137. Cyanide of propylene its preparation and conversion' into pyrotartaric ncid 139.Cymole conversion of caoutchin into 119. -conversion of the from turpentine and caoutchin into inealinic acid 121. D Dancer W. on hypohromoua acid 477. Daubeny C. B. supplementary note to R memoir on the power ascribed to .the roots of plants of rejecting poissn- OUR or abnormal substances presented to them 16. Decomposition recsiprocal among salts in solution additional notes on by J. H. Qladstone 302. -in alcohol 307. -testimony of from difiaion experi-ments 308. Doh Rue,%arren and Hugo Muller on the resin of Ficus mbiginoaa and a new homologue of benqdic alcohol 62. Dextrin dialysis of 258. Dialysers 220 239. Dialysis 219 237. -through animal mucous 243.-through parchment-paper 242,243. -preparation of colloidal substance8 by 248. -of organic colloid substances 256. Dichloride of ethgl-sparteine 7. Diffusion on liquid applied to analysis by T. Graham 216. -of albnmin 224. -in alcohol of a solution of resin, 228. -of caramel 224. -of chloride of sodium 222,226,227 230 231 232 234 236. -of gud 222. -of hydrochloric acid 227. -of sugar 222 226. -of tannin 222. -effect of temperature on 235. Diffusion experiments testimony of reci-procal decomposition from 308. -of a mixture of chloride of potas. eium and chloride of sodium 230. _-of a mixtiire of chloride of potaa-sium and sulpllatc of soda 284. ~ of n mixture of chloridc of sodium and sulphaie of potash 234.-of mixtures of chloride of sodium with the sutphates of soda and potash, 231 232 234. -of iodine and acetate of potash in akohcl 223. Digewion on tlie chemistry of by W. Marcet 407. Oihydrate of boric dioxgethide 371. Dioxyethide boric 370. Divers E ,on the action of carbonato of ammonium on magnesian salte 196. Donations to thc Library of the Chemical Society (1 862) 506. Dumas' method of taking *pour-den- sits modification of by Play fair and Mauklyn 149. E. Elements atomic weiehts of 390. -in solittion ultimate disposition of independent of original mode of com-bination 302. Emulsin dialysis of,261. Emiilsioning of fats by the pancreatio juice 416. -of fatty acids by the bile 416. Ethyl iodide of its action on ethyl-sperteine 7.-iodide of its action on sparteine 5. -nitrate of its vapour-density 163. Bthyl-sparteine. 5. -action of iodide of ethyl on 7. Ethylene cyanide of action of nitrate of silver on 137. -cyanide of action of nitric and hy-drochloric acids on 137. -cyanide of action of potash on, 136. -tyanide of its preparation 165. -hydratfs of oxide of 394. -on oxide of considered as a link between organic and mineral chemistry by A. Wurtz 887. -oxidation of oxide of 398. Emulsioning of fatty acids by tribasic phosphate of soda 4 16. Emulsions formction of accompanied by partial saponification 416. Erlenmeyer Dr. and J.A. Wanklyn on the constitution of rnelampyrin 456. 618 IKDEX.Erytbromannite action of hydriodic acid on 161. Ether determination of its vapour. density 147. _I percliloric note on by 11. E. Roscoe 213. Ethers capillary transpiration of 439. Ethide ammonia-boric 3CO. I_ boric 367. Ethyl action of zinc-ethyl on borate of 367. -borate of action of zinc-methyl on 375. .-hydropiperate of 25. Ethylene oxide of its compoundrJ with ammonia 405. -oxide of its compoui~ds with acids 398. Evacuation alvine object of 418. Excretin its relation to ctlolesterin 41 8. F. Fats nentrd emulsioning of by the pancreatic juice 416. Fats neutral their transformation into fatty acids in the stomach 414. Fatty acids emu1f;ioniag of by the bile and pancreatic juice 416.-emiilsioning of by phosphate of soda 115. Ferricyanide of iron dialysis of 253. Ferricyanide of copper dialysis of 251. Pims rubiginosa on the resin of by Warren De la Rue and Hugo Miiller 62 Field F. on the double sulphides of copper and iron 125. Fire bricks determination of silica and titanic acid in 822. Fire-clays and Fire-bricks on the de- terminationof alkalies in by G. Gore 104. Pormate of ethyl capiilary transpiration of 439 Formate of lead note on the sulphur- compound formed by the action of sulphuretted hydrogen on at a high temperature by W. J. Hurst 278. Foster G. C. on piperic and hydro- piperic acids 17. Frankland E. on the influence of at-mospheric pressure on some of the phenomena of combustion 168.-on a new series of organic com-pounds containing boron 363. G. Gastric juice acidity of 410. -its action on polariwJ light 41 3. Gsg-Lussa.c'emethod of talcin vaponr. densities modification of by flay fair and Wanklyn 143. Qladstone J H. addit>ional notes 011 the reciprocal decomposition amongst salts in solution 302. Glyceriii car illary transpiration of 441. Gold-salt of berberine 315. -of sparteinc 3. Gore G. on the dctermination of al-kalies in fire-clay and fire-bricks 104. Gore a. on the properties of liquid carbonic acid 163. Oraham Thomas Oil liqiiid diffusion applied to analysis 216. -. on capillary liquid transpiration in relation to chemical coniposition 427. Ground ice on by 11.Adie 88. Gum dialysis of 257.Gum diffusion of 222. Harcourt A. Vernon on a method for the determination of nitric and nitrous acilts. 381. Heat its action on sporetin 66. Hei n tz Profemor on the composition of the amorphous deposit in healthy urine 467. Heptyl hydride of from cannel coal 423. Hexbromide of anthracene 49. Hexyl hydrate of fram cannel coal 422. Hexyl iodide of its formation by the action of llydriotlic acid on melam. pyrin 458. fTexylic alcohol 461. Hoop dialyser 220. Hurst W. J. notes on the sulphur-compound formed by the action of sulphurretted hydrogen on formate of lead at a high temperature 278. Hydrates of oxide of ethylene 394. Hydropiperate of barium 23. -of calcium 22. -of ethyl 23. I_ of potaesium 21.-of silver 23. Hypobromous acid on by W.Dancer 477. -anhydride attempt to prepare 485. Hyposulphite of berberine and silver 347. Hydride of amyl from crtnnel coal 421. -of heptyl (oenanthyl) from cannel coal 423. -of hexyl (caproyl) from canncl cod 422. -of octyl (capryl) from cannel coal 425. Kydrides of the alcohol-radicles on the existing in the products of the distil- lation of cannel coal by C. Schor-leplmer 419 INDEX‘ 619 Hydriodate of berberine 351. -of biniodoberberine 352.. Hydrobromate of berberine 350. Hydrocarhons on the produced by the destrudive distillation of Boghead coal by C. Gr. tvilliams 130. -relation between the first and second produced by distillation of caoutchouc 116.Hydrogen note on a method of affecting the substitution of chlorine for in or- ganic compoonds by 11u g o hl ii 11e r 4!. Hgdropiperate of ammonium 21 I. ]Ice colloidal characters of 268. -on ground- by R. Adie 88. Iodide of ethyl :ita action on ethyl-spar-teine 7. -of-ethyl its action on aparteine 5. Iodide\ of hexpl obtained by the action of hgdriodic acid on melampyrin 458. -of sparleine 3. -of zinc and sparteine 4. Iodides of the alcohol-radicle8; their formation from * Bogliead na&ha hy C. Or. Williama Iron determination of by stsndard eolu- tion of bichtomate of potaab 329. -dialysis of ferridcyanide of 2651. -dialysis of sucrate of qeroside of 253. dircct determination of in iron ores 336.Iodine diffusion of in alcohol 228. Iron and copper on the double sulphidee of:by F. Field 126. Iron copper and potassium ona complex cyanide of by W.J. Wonfor 367. Iron,volumetric estimation of in watem 474. Iron ores on the analysis of and 01 silictous minerals containing iron ; the separation of oxide of iron from titanic acid an8 the met.hcda of mtimating iron by E. Riley 311. -titanium in 339. -oolitic analyses of 535. Iron eesqiiioxide of ita determination when hired with aluniinr and titanic acid 331. -aesqnioxide of and alumina eepa ration of by potash 331. -sesquioxide of and titanic acid experiments with 326. -sesquioxide of and titanic acid separation of 332. -sesquioride of alumina,and ti-acid separation of 333.[ron soluble metaperoxide of 250. -soluble peroxide of; preparation by dialysis 259. Iron-stone bastard technicfilly known 88 “Jack,” analysis of 323. Isoprene action of atmospheric oxygen on 115. -action of bromine on 118. -and caoutchin on by C. Or. Wile liams. -end caoutchin polymeric relationa of 117. -and caou tchin table of their phyei- cal properties 123. J. Jar-diffusion 22 I. Jones H. Bence on thecompositionof the amorphous depit of umtes in healthy pine 201. -on a deposit of cryetallised ranthin In human urine 78. -on the Occurrence of crystalliaed phosphate of lime in hnman urine 8. -on the simultaneous variationa of hippuric and uric acid in healthy urine 81.K Kaolin American containing titanic acid analyses of 323. Eolbe Hermann on the chemical composition and artificial formation of taurine 94. L Lead arsenite of 291. -on the eolubility of its sulphate in hydrochloric and nitric acids by Q. F. Rodwell 69. -and tin on aome physical properties of the alloys of by Profeeeor Bolley 80.-Remarks thereon by A. Mat-thiessen 106. -tin antimony and copper ahalyms of alloys containing 462. Letheby H. on the production of a blae eiibstance by the electrolysis of d-phate of aniline 161. Library of the Chemical Society done tions to (1862) 606. Light of combustion influence of com-preasion of the air on the 187. -of combust,ion influence of rare-faetion on 177. Lime action ’bf bromine on hydrate of 478.-dialyeie of sucrrte of 264. Lime,on the occurrence of cnnelderable depoeita of crjstallised phosphate of, in tcsk-woo& by F. A. Abel 91. on the occurrence of depoeite of cry&dlised phoeplr:,te of tn human urine hy 11. Uencc Jonccl 8. --volumetric tetirilatioil of in wntcr 4i2. IIoric mcthidc 360. Liqtiid rlitt’ueion a; plied to nnnlpis hy T.Oraham 216. M MRgncsia aracnite of 294. Magne$ia volumetric estimation of in waters 472. Magnesian salta on the influence of car-bonate of ammonia on. Ly E.Divers 196. Magnesium and ammcmium carbonate of 199. \ Marcet W. on the chemistry of di-gestion 407. Matter co1lo:dal condition of 265. Matthieasen A. note on Profeesor Bollcy’e commiinication “ On some physical propertiea of the olloje of tin’ and lend.” 108.Mecorrinc 451. Meetings ot the Chemical $~iety pro- ceedings at the 4S9. Melampyrin action of hgdriodic acid on 4.)8. -on the constitution of lby Dr. Erlerimcyer and J. A. Wanklyn, 45G. Melting points of nlloje of tin and lead 32. Mercuv action of bromine-water on oxide of 451. -action of bromine on dq oxide of 488. Metalumina aoluble preparation by di;ll)sis 248. Metnnaphtlialin 4 4. hlentliyl butJr;itc of 27. -clilorille of 27. Metaperoxide of iron solulle 250. Metxhtannic aoid dialjsie of 266, Methide ammonia-boric 377. -boric 853. -boric its compounds with potash, soda limc and batFta. 379. Mentllol or mentholic alcohol 20.Methylic alcohol capillary transforma tion of 439. i 11R E. J. on sparteine 1. Morphine 450. MUCUS,animal dialjsia through 242. Mliller Hugo note on a method for affecling the aubstitution of chlorine for hydrbgen in organic compounds 41. -Hugo and Warren De la Rue on the rcsiti of Ficzce rubiginoan and a new homologue of benzylic alcohol 62. N. Narceine 462. Narcotinc 45‘2. Newlands J. A. R. on the con-struction of tablcs exhibiting the composition and mutual relations of orgnnic bodice 88. Nicholeon E. on a volumetric procees for the annlgsir of waters 468. Nitrate of berberine 318. -of ethyl it3 vayour-density 153. -of eilver action of bromine-wd,er 011 479. -of silver ite aclion on cJanide of ethylene 137.Nitrogen peroxide of ite vapour-density 156. 0. Octyl hydride of from cannel coal 426. Ocnantliyl iodide of from Uoghead naplitlin 361. Oenanthjl:imine platinum.dt of 361. Oolitic iron orea analyses of 336. Opianine 466. Opianyl 458. Opium on the chemistry of by T A rid erson 446. Opium bases are they products or eduets? 455. Oppenheim A. on the camphor of -peppermint 24. Optical rotatory power of peppetmint camphor 26. Oree oolitic iron- analyeer of 385. -iron titanium in 880. Organic colloid rubstaocea dialysis of 256. Organic CompoundE on a method of effecting the eubstitution of chlorine for hydrogen in by Hugo Bfiiller 41. -compounR8 on a new series of containing boron by E.Frankland 863. -matter determination of in iron ores 338. -eubstanees on the construction of tatdea exhibiting the composition and mutual relation8 of by J. A. R N ew-lands 36. INDEX. 52 I Omaee 269. Oxalate of eparteine 8. Oxanthracene 48. Oxide of ethylene conaidered aa a link betweenorganic and mineralchemietry ; by A. W urtz 387. -of ethylene it! compounds with acids 398. -of ethylene! ita compounds with ammonia 405 -of ethylene hydrates of 394. -of ethylene oxidation of 393. -of mercury action of bromine-water on 481. -of mercury action of bpmine on dq 483. Oxyethglenic bases 405. Oxygen action of atmoepheric on iao-prene 11 6. Ozone its action on iaoprene 115. P. Pancreatic juice :ita powerof emulaioning neutral fats and fatty acids 416.Papaverine 452. Paracymole conversion of caoutchin into 119. Pwanapththalese 45. Paranapthalin on the conetitution of by T Anderson 44. Parchment-paper naed m a dialper 220. Pectous modification of fluid collo'ida 217. Pelargonamhe platinmndt of 362. Pelargonyl iodide of from Boghead naphtha 962. Peppermint on the amphor of by A.Oppenheim 24. Feptone polariaing 418. Peroxide of iron dirlyris of wmah of 268. -of iron mluble preparation by dialyeis 249. -of nitrogen ita vqmr-density 166. -of tin dialpie of 256. -of uranium dialyaia of mcrate of 254. Yerrina J. D. on berberine contribu- tions to its hiatory and revieion of ite formula 339.Pboaphate of lime on the occurrence of depoaits of cryatallieed2 in human urine by H.Bence J onea 8. Phipson T.L,on sombrerite 277. -on the transformations of oitric butyric and valerianic acids with refe-rence to the artifioia\ prodacthn of succinic acid 141. Phoephate of lime on the occurrence of considerable deposita of crystallised in teak wood by F. A. Abel 91. Phoephorua action of chloride of on sycocbrylic alcohol 73. Pipcric and hydropiperic acids on by 0.C. Foster 17. Piperate of barium 18. -of potassium 18. Plants supplementary note to a memoir ion the power ascribed to the roots of of rejecting poieonous or abnormal substances presented to them by C. B. Daubeny 16. Platinum-salt of amylamine 361.-of berberine 314. -of capqlamine 361 -of ethyl.eparteine 6. -of enanthylamine 361. -of pelargonamine 363. -of eps'rieine 6. Playfair Ljon and J,'A Wanklyn on a mode of taking the vaponrdenaity of volatile liquids at temperatumbelow the boiling point 143. Polarised light action of gastric juice on 413. Polarising peptone 413. Polarisation circular method of testing reciprocal decompoeition by 308. Porphyroxine 465. Potash action of bromine on 478. -diffusion of'acetate of in alcohol 228. Potash-boric methide 379. -quadrarate of 212. Potaeh and soda action of arsenious acid on the carbonates of at 212" F. 281. -at a low red heat 287. Potassium hydropiperate of 21. -and sodium diffusion of a mixture of the chlorides of 230.-iron and copper on a complex cyanide of by W. J. Wonfor 357. Pressure of the atmosphere; ite influence on the light of combustim 177. -ita intluence on the rate of combas-tion 170. Proceedinge at the meetings of the Cbemi- cal Society 483. Propglene cyanide of its preparation and conve:eion into pyrotartaric acid 139. Pruesian blue neutral dialysis of 253. Pseudomorphine 455. Pyrene 44. Q* Quantitative determination by circular plariSation 508. 522 INDEX. Quadrurate of potarssa 212. R. Rarefaction of the air ; its influence on the light of combustion 177. Rate of combustion influence of atmos-pheric pressure on Reciprocal decomposition in alcohol 307. -testimony of from diffusion expe- rimenta 309.Report of the President and Council of the Chemical Society (1862) 492. Resinj diffusion in alcohol of a solution of 228. Resin of jcwl rebiginoea on the by Warren De la Rue and Hugo MUller 62. Retisterene 44. Riley E. on the general Occurrence of titanic acid in clays and the method employed to estimate it; on the ana-lysis of iron ores and silicious minerals containing iron the separation of oxide of iron from titanic acid and the methods of estimating iron 311. Rodwell G. F. on the solubility of sul-phate of lead in hydrochloric and nitric aids 59. Roote of plants. supplementary note to a memoir on the power ascribed to the of rejecting poisonous or abnormal sub-stances presented to them by C.B. Daubeny 16. Roscoe H. E. on the composition of the aqueous acide of constant boiling point 270. -note on perchloric ether 213 S. Salta of sparteine 3. Schorlemfner C. on the hydrides of the alcoholradicles elieti g in the product8 of the destructive lhtillation of camel coal 419. Sediment decomposition of the ordinary amorphous in urine by waahing with water 206. Sequioxide ef iron determination of *hen mixed with alumina and titanic acid 331. -and alumina separation of by pot aeh 331. -and titanic acid separation of 332. -alumina and titanic acid separa- .tion of 333. Silica estimation of in waters 474. -obeervations on by A. H. Church 107. Silica. and titanic acid dotermination of in fire-bricks 322.Silicate of gclatin 246. Siliceous minerals containing iron on the analysis of &c. by E. Riley 311. Silver action _of bromine-water on the nitrate of 479. -arsenite of 200. -and berberine bypoeulphate of 547. -hydropiperate of 23. -nitrate of; its action on cyanide of ethylene 137. Simpson Maxwell on the synthesis of succinic and pyrotmtaric acids 134. qlag from blast -furnace composition of 314. Smy t h Professor ; note on the compo- sition ofa boiling spring in New Zea-land 57. Soap preparation of alcoholic solution of for water-analysie 471. Soaps passage of through membranes 416. Soda action of bromine on 476. -and potausa action of arsenious acid on the carbonates of at 212" F. 281. -at a low red heat 287.-diffusion of mixtures of sulpbate of and the chlorides of potaseium and sodium 232 234. Sodaboric methide 380. Sodium its iebion on peppermint-cam-phor 28. -chloride of ib diffusion 222 225 227 290 231 232. 234 236. -diffusion of mixtures of chloride of with the sulphates of &a and potaah 236 232,234. -and potassium diffusion of a mir-ture of the chlorides of 230 Soils containing titanic wid from Weet lndia islqnds analyses of 323. Solvents acid action of 307. Sombrerite,on by 'l'!L:Phipson,277. Sparteine on by E. J. M i I1 a 1. -action of iodide of ethyl on 6. -and zinc chloride of 6. -and dnc iodide of 4. -salts of 3. Specific gravitiea of the alloys of tin and lead 3 1. Spring on the composition of a boiling, in New Zealand by' Professor Smy t h 67.Steam-boilers new experimenta on the dangers arising from the use of cer-tain waters for feeding by Professor Bolleg 32. Stomach ; its power of converting neutd fats into fatty acids 416. INDEX. 8umta of copper dialph of 265. -of lime dialfie of 364. -of peroxide of iron 253. -of peroxide of uranium dialyb of 254. Sugar diffusion of 222 226. Sulphate of lead; on its solubility in hydrochloric and nitric acids by 0. F.Rodwell 59. -of eoda diffusion of mixtures of with the chloricla of potassium and sodium 234. Sulphides on the double of copper and iron by F. Field 126. Sulphur determination of in iron orea 337. Sulphur-compound note on the formed by the action of sulphuretted hydro- gen on formate of lead at a high tem- perature by W.J. Hurst 278. Symons W.,description of a combined maximum and minimum mercurial thermometer 299. 8ycocery1 acetate of 67. Sycocerylic alcohol 71 Sycoceryl benzoate of 74. Sycoretin action of heat on 66. -action of nitric acid on 66. Sycoretin action of sulphuric acid on 65. T. Tables on' the construction of exhibiting the composition and mutual relations of organic substances by J A. R Ne wlands 36. Tannin dialysis of 256. -difhsion of 222. Taurine on the chemical composition and artificial formation of by Her- mann Kolbe 94. -formation of from chlorethyl-sulpburic acid 101. Teak wood on the existence of con-siderable deposits of cryetallised phos- phate of lime in ; by F.A. Abel 91. Temperature :its effect on difhsion 236. Teriodide of berberine 352. Tetrabrominated anthracene 50. Thebaine 451. Thermometer description of a corbined maximum and minimum mercurial by W. Symons 299. Time-fuses combustion of influence of atmospheric pressure on its rate . Tin dialysis of peroxide of 255. -and lead on Borne physical properties of the alloys of by Professor Bo 1I e y, 80.-Remarks thereon by A. Mat-thiessen 106. -lead antimony and copper awiysip1 of alloys contsining 461. Tin,on the separation of from antimony. by C. Tookey 462. Titanic scid on ita gene& occurrenm in clays and the method employed to atimate it; the separation of oxide of iron from titanic acid &c.by E Riley 311. -acid and ammonia experinienta with 327. -acid and alnmina experimente with 326. -acid alumina and sesquioxide of of iron separation of 333. -acid preparation of pure,-824. -acid and eesquioxide of iron perimenfa with 826. -acid and seequioxide of iron eeparation of 832. -acid and silica determiwtion of in fire-bricks 314. -acid dialysis of 256. -acid special experimenta with 826. Titanium in iron ores 339. Tookey Charles on the separation of tin from antimony and on the analysie of alloys containing lead tin antimony and copper 462. Transpiration on capillary liquid in re-lation to chemical cornposition by T. Graham 427.Turpentine oil of and caontchin com-parative exprimente on the action of bromine on 117. U. Uranium dialysie of sucrate of peroxide of 254. urates artificial foAation of compounds of the which are decomposed when washed with water 209. -on the composition of the amorphous deposit of urates in healthy urine :by H. Bence Jones 201. Urine on the composition of the amorphous deposit of uratesin healthy by H. Bence Jones 201. -on the composition ofthe smorphoua depoeit in healthy ; by Profecasor H eintz. -human on the Occurrence of de-posits of crystallised phosphate of lime in by H. Bence Jones 8. -decomposition of the ordinary amorphous sediment in by waahing with water 206. -on a deposit of crystdiaed xanthin in human; by H.Bence Jones 79. -on the simultaneous variations of hippuric and uic acid in healthy by M. Bence Jones 81 V. Valerate of ethyl capillary tranaformation of 439. Yapour-densities modification of Dud mas’ method of taking by Play-fair and Waklyn 149. -modification of Gay -Luseac’s method of taking by Playfairand Wanklyn 143. Vapour-density of alcohol 145 146 162. - of aqueous ammonia 160. -of nitrate of ethyl 153. -of nitric acid 154; -of peroxide of nitrogen 166. -on a mode of taking the of volatile liquids at temperatures below the boiling point; by Lyon Playfair and J.A. Wanklyn, Vegetable parchment uaed aa a dialyser 220. W. Wank1y n J. A. and Dr. Erl e nm eyer on the constitution of melampyrin 456.Wanklyn J. A.,and Lyon Playfair on a mode of taking the vapour- densities of volatile liquid8 at tem-peratnreabelow the hiling point 143. Waters,new experiments on the dangers ariaing fmm the use of certain for feeding steam-boilem by Profemor Bolley 32. 1N DEX. Water from a pump at .FortPitt analyeis of 475 -supplied by the Chatham Water Company to Fort Pitt analysis of 474. -solubility of bromine in 487. Waters on a volumetric process for tl!s analpis of by E. Nicholson 477. Williams C. Greville on the forma- tion of the iodides of the alcohol-radides from Boghead naphtha 359. -on the hydrocarbone produced by the destructive distillation of Boghead coal 130. -on isoprene and caoutchin 110.W onfor W. J. on a complex cyanide of iron copper and potsseium 357. Wurts Adolphe on oxide of ethylene considered aa a link between organic and mineral chemiatry 887. x. Xanthin on a depoait of cryatallieed in human urine 78. Z. Zinc araenite of 296. -and sparteine chloride of 6. --iodide of 4. Zincethyl :its action on borate of ethyl 367. Zinc-methyl ha action on borate of ethyl 375. WTNTED BY If&RRISON AND BONR BT. MARTIN’S UNE W.C.

ISSN:0368-1769    

DOI:10.1039/JS8621500513

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

524 1 N DEX. ERRATA. Page 394 foot-note for Methode de Chemid read Mdthode de Chimi e. Page 396 he 6 from bottom,for diethlyic read diethylic-, 402 , 3 from bottom for chioraceten read cldcmcetin. . @8 , 5 from top dele ccfour.” -~ WTNTED BY If&RRISON AND BONR BT. MARTIN’S IANE 1V.C.

ISSN:0368-1769    

DOI:10.1039/JS8621500524

出版商:RSC    

年代:1862

数据来源: RSC