UNDERGRADUATE ORGANIC LABORATORY CHEMISTRY* IZZA.
Diversification, Relative Importance, and Comparative Cost of Laboratory Experiments
E. F. D E G E I ~ N GR. . F. MCCLEARY, AND A. R. PADGETT Purdue Universitv. Lafayette, Indiana
A classified list of experiments on laboratory operations and on the peparations and reactions of c o m m a aliphatic compounds is presented. Current manuals were used i n the compilation of the list. The cost of each experiment, based on a group of one hundred students, is giuen.
+ + + + + +
T
HREE considerations have prompted the preparation of the following outline. But few, if any, will deny that there is a tendency on the part of even the best instructors to develop a stereotyped
-
* Inarticle "11. The Laboratarycourse," J. CHEM.Eouc., July, 1933, p. 434. column one. lines 21-4 should read, "The student then places the record of the specific experiments on alcohols on the right-hand page, just opposite the general equation outline."
course. While some may, for various reasons, actually prefer a stereotyped course, it is hoped that the accompanying outline of experiments will offer sufficient diversification, without undue cost, to awaken new interest on the part of the students and thus instil new life into the laboratory course. But along with the item of diversification, one must also consider the relative importance of an experiment. The writers have assumed that perhaps one of the best criteria of the relative importance of experiments is the periodicity of their inclusion in the current laboratory manuals. While individual authors may select certain experiments from a given group, it is apparent that certain groups of compounds are emphasized more than others. Hence it would seem that the accompanying list of manual references should serve to guide the
instructor to place the emphasis in his course on the more important classes of compounds. A third consideration deals with the p d e n t question of comparative cost of experiments. From the tabulated data it is apparent that single experiments may range in cost of performance from a few cents to several hundred dollars. The determining factor, then, in the selection of an experiment must necessarily be whether the additional technic acquired by its performance justifies the additional expenditure. With this thought in mind, each experiment has been carefully checked in so far as the required chemicals are concerned, and the cost of each experiment (based on a group of one hundred students) calculated and tabulated in the following outline. The particular manual used in calculating the cost of each experiment is indicated. Hence it is hoped that the outline will prove of material assistance in helping instructors to adapt their courses as advantageously as possible to their allowable expenditures without sacrificing the more important types of procedures. In the preparation of this outline, no consideration has been given to the use of student preparations in any of the experiments, all costs having been based upon purchased chemicals. Obviously the use of student preparations tends to lower the cost of chemicals. For this reason the authors favor series of experiments whenever possible. Such a practice also tends to-prevent the accumulation of student preparations. Technical chemicals have been figured except where C.P. chemicals were specified by the manuals. Where definite amounts of chemicals were not specified by the manuals, estimates have been made. In any event, the prices given in the outline are to be considered as approximations despite the fact that the list was checked quite carefully. No attempt has been made to compare similar experiments on a yield basis. In the preparation of absolute
A.
alcohol, for example, the costs by the use of calcium oxide and by benzeneareS16.12 and $7.00, respectively, these costs being based upon the amounts called for in the experiments cited. On a comparative yield basis, however, the cost of the latter experiment would be about $10.40. The outline is based on the following current manuals, which were selected without prejudice as being representative of the work that is being offered in organic laboratory courses; ( A ) ROGER ADAMSAND JOHNR. JOHNSON,"Laboratory experiments in organic chemistry," rev. ed., The Macmillan Co., New York City, 1933; (F) HARRYL. FISHER, "Laboratory manual of organic chemistry," 3rd ed., rev. ed., John Wiley &Sons, Inc., New York City, 1931; (G) L. GATTERMANN, revised by HEINRICHWIELAND, "Laboratory methods of organic chemistry," The Macmillan Co., New York City, 1932; (J)LAUDER WILLIAM JONES,"A laboratory outline of organic chemistry," rev. ed., The Century Co., New York City, 1914; (L) ALEXANDER LOW AND WILMERE. BALDWIN, "Laboratory book of elementary organic chemistry," John Wiley &Sons, Inc., New York City, 1931; ( M ) HOMER ADKWSAND S. M. MCELVAIN,"Practice of organic chemistry," 2nd ed., McGraw-Hill Book Co., New York City, 1933; ( N ) JAMES F. NORRIS,"Experimental organic chemistry," 3rd ed., McGraw-Hill Book Co., AND New York City, 1933; ( W ) ROGERJ. WILLIAMS RAY Q. BREWSTER, "Laboratory manual of organic chemistry," 3rd printing, D. Van Nostrand Co., New York City, 1930; (D) FARRINGTON DANIELS,J. HOWARD MATAEWS, AND JOHN WARRENWILLIAMS, "Experimental physical chemistry," McGraw-Hill Book Co., New York City, 1929; (C) MILE MONNIN CHAMOT AND CLYDE WALTERM~s,o~,~"Handbook of chemical microscopy," John Wiley & Sons, Inc., New York City, 1930; and current journals. (Page numbers iustead of experiment numbers are given for references to DANIELS, to GATTERMANN, and to CHAMOT.)
Lobaolory o#notions
1.
Purification of organic solids
2.
Purification of organic solids by: a. Deeolmization b. D i ~ l y s i s c. Diptillation, fraetiooal
d. f.
Distillation, steam Distillation, vacuum Dryins
8.
Extraction
h.
Filtration from solvent Deeamporition of derivative. Precipitation Recrystallization
a.
i. j
k.
..
2
..
. 20
33.39
SB 44 590, p
42 37.49 43
.
..
26
.. 8 ..
14.17, 118 26 19,140 12,181
..
108 95 45
.
57 59 25
..
If 1c 25
11 p. 170 p. 112
.. 92 30,'d3, 84 80 81.82 89
..
..
110.14 0.22 0.41 5.34
(Total)
14 161 214,45 28-30 24-7 36,37
2 134 66
W2 L lc F 26A
155 163 187
1.20 A SB 9 . 9 6 G 140 9 . 0 0 G 181
..
..
0 . 0 0 Library
I. 3. 4.
Salting out m. Sublimation n. WarhiW Determination of purity of organic wlidn Determination of purity of organic solids by: a. Boiliog point b. Melting point r . ~ e f r a e t i v cindex (D. p. 324. C. v. 1. p. 369)
..
..
..
..
..
..
J 13
Calibration of thermometer by mdting points
.. .. ..
Purification of mgaoic liquid* Purification of o r. m i e liauids by: Decantation Drcolorizntion Distillation, dircet
9 56
L
M 3
..
.. ..
10 10
N 8
.. .. ..
15.92 35.79
48-52
W 5
..
..
..
..
..
. .6
Cart 1.70
Ref. W5
0.00 Library
124.22 (Total) . . 150,168 3.53 W 150 1390 31 37.10 N 1390 15-20. 20 2.95 8 8
Distillation, fractional Distillation, steam Distillation, vnevvm Drying Evaporation of lighter solvent Extraction Filtration Freezing Salting out Warbing with sn immiscible liquid Determination of purity of organic liquids
.56.
.
Determination of purity of organic liquid. by: Boiling point (mim.3-) b Freezing point c. Refractive index (D. p. 324, C. v. 1. p. 369) d. Specific grnvity or density
.. 4 la
.. .. ..
.. ..
..
..
..
7 93
..
93
44
..
..
56
144
.. ..
4.58 (Total) 1.60 F 2 0.45 W 144 0.34 D 324 2.19 D 23
0.00
Calibration of a thermometer by bailing point Identification of elements in orsanie compounds Qualitative organic annlyris. "known"
3.8. 44 3. 8. 44
Qualifstive organic analyib, "unknown"
.. .. .. ..
Quantitative orgaoie analysis Qunalifnfivc organic analyrir Nitroxm by the Uumar method o C and H by ~implilierlmrfhcxl h L.
..
..
..
2
5.6
57-81
2
5. 6
57-61
7-10. 100 7-10. 100
.. .. .. ..
.. .. 94 94
.. .. .. ..
.. .. ..
..
Library
1.68 A 8 1.68
A 8
0.00
Library
73.09 (Total) 41.29 G 45-52 4.18 C. A . IS,
Determination of S, X, ete.
preparation of Grignard% reagent Determination of the iodine value a.
b C.
.. .. .. .. .. ..
Hydrogenation with palladium 1. With Skita's eolloidsl estnlyst 2. With catalyst depo~itedon a carrier Catalytic hydrogcnaflon with nickel Replacemcot of 0 of carbonyl with H 1. Acetophenone t o ethyl benzene 2. Bcnzil to dibcnzyl
.
.
..
.. .. .. ..
137 137 137
.. ..
.. .. .. ..
..
..
137
.:.
.. .... .... .. . . . .. .. .. .. ..
23.50 13.81 9.69 14.75 45.04 4.74
(Total) G 367 G369 G 370 (Total) G 374
Prc*worionr end rrodions of olioholic ronr~oundr o.
Properties of the saturated hydrocarbons
1. Methane from sodium leetlte 2. Methane from chloroform 3. Methane from nlvminum enrbidc c. Ethane from ethyl halides d. D ~ a n from e amyl bromide U. Cmar. Eouc.. 7, 2712 (1930)l c. Di-iroamylfromisoamyl bromide f. Fractional distillation of petroleum g. Dcotrudivc distilletion of soft coal b
e.
f. 8.
h.
.. .. .. ..
Dimethyl ethyl csrbiool from acetone DiCthyl methyl carbind from butanone-2 Allyl alcohol from glyeeml Pinaeol hydrate from acetone
properties of the olefiner 1. Ethylene from ethanol by HnSOa 2. Ethylene from ethanol by HIPOI 3. Ethylene fram ethanol by PzOr 4. Ethylene from ethylene dibromidc . ~ m y l e n ;from nmyl alcohol d. laopreoe and its polymen a.
b.
n. Properties of the aeetylenu
6.
1. Acetylene from calcium carbide 2. Acetylene from ethylene dibromide
..
7 32
.. 74
..
..
.. .. .. ..
50.08 1. Cn. Eo. 22.48 N 74 0.20 L 7 0.14 L 3 2
B . Praparnrionr and reaclionrof olipholic rornpoundr (conl.) 5
. 0. b
..
1. Methyl bromide from methanol 2 . Methyl iodide from mcthanol 1. Ethyl bromide from ethanol
.. .. ..
. . 221...
C
d
r.
f. 6
.
Ethyl iodide from ethanol n-Butyl bromide from bufanol n-Butyl chloride from butan01 Amy1 bromide from p~ntanolIJ C a e r Eouc.,
.
.
1. . I 2712 (1930)l 2 . Iso-amyl bromide from iso-amyl alcohol 1. Chloroform from acetone 2 . Iodoform from ethanol. efc .
. Ethylene dibromide from ethylene . Properties of ethers b . 1. Diethy1 ether from ethnaol 2 . Absolute ether 9, c. Dibntyl ether from b u t a d [J . CRBM. EDUC., 9
n
1268 (1932)l
d . Iso-amyl ether from iro-amyl alcohol r 1 Methylme dicthers (mbhylal) 2 Hydrolysis of methylene dicthers
. . .
b . 1. Formaldehyde fram methanol. by CuO 2 Pornaldehyde from methanol. by Pt
..
Formaldehvde-liluer nitrate cell
.
Acetaldehyde fram acetylene
3
.
1. ~ e e f a l d e h i d efrom paraldehyde 2 . Acetaldehyde from ethanol 3
d
.
.
4 . Acetaldehyde from aldehyde ammonia 5. Acetaldehyde from metallic formate "-Bufyrsldchyde from butan01 Furfvral from oentorer
. 8 . o. Properties of ketones
b r
.
.
A
Properties of dkyl halides
Acetone from ea1eivm acetate Heptaoonrz from ethyl n-butylacetoacetate
d. Acdyl acetone from acetone
9 . Chloral from chloral hydrate 1. Formic acid from methanol 2. Formic aeid from oxalic acid 1. Glacial acetic acid from sodium acetate
Free fatty acid* from fats
1. properties of esters 2 . properties of acetoacetic utera Methyl formate 1 Ethyl acetate from ethanol 2 Ethyl acetate by slaw distillation ' 3 Ethyl acetate from acetyl chloride Ethyl acetate from acetic anhydride 4 n-Butyl acetate from butanol 1so-amy1 acetate from sodium acetate 1 Diethyl malonate from monoehloroacetie aeid 2 Diethy1 ethyl ma1onate from l l . f . 1 Diethyl n-butyl malonatefromdiethylmalonate 1 Acetoacetie ester from ethyl acetate 2 Ethylacetoacetic ethyl ester from 1 l . h . l Ethyl n-butylaeetoseetate 1 Ethvl oxalate I J A m Chsm Soc KS 3560 ( i m ) . iho a&ts.~ 2 Methyl oralate from oralic acid Glycol diacetste from ethylene dibromide Glycin ethyl ester hydrochloride
. . . .
. . . . . .
.
.
.
..
..
propertie of amides 1 Aeetamide from glacial acetic acid 2 Acetamide from ethyl acetate Properties of acid chlorides Aeetyl chloride from acetic acid Properties or anhydride Acetic anhydride from acetyl chloride SucFinic anhydride from succinic acid
. .
.
.
Prop~rtiesof cyanide Methyl cyanide from acetamide Butyl cyanide from n-hutyl bromide Formation of an iso-cyanide
.
Properties of fatr. salts. and mapa
soao from fats
.
14
.15b.
