85

When organic solvents are used in estraction processes, it is often necessary to de-
termine small amounts of esters or alcohols in the organic or aqueous phases.
I;axcL*~” mentions a spot test for alcohol as follows: vanadium(V) forms a complex
with osine3*” in an acetate medium, the ratio of vanadium to osine being I : 2. The
compltzs is insoluble in water and acetic acid but dissolves in benzene, chloroform,
acetone, alcohol and trichlorethylenc, giving a dark qeyish-green colour to the
organic phase.
If alcohol is added to the suspension of the vanadium complex in water and an
estraction with benzene is carried out, the organic layer appears red. It is presumed
that a second comples with the alcohol is formed (II) which is more stable than the
initial ~wiaclium osine comples (I).

NT
55
s 0
_-.
() . . -~ i’ I .. ..--_- (- -

8 I ‘\
OII
I

(J s
/I

This secondary complex (II) is formed with primary, secondary and tertiary alcohols
but not with alcohols containing a phenolic or carboxylic group (citric or lactic acid,
phenol) escept where the carbosylic group has undergone esterification e.g., the ester
of lactic acid.
BUSCAROXS, MARIN AND CLAVER~ esamined the colours obtained by dissolving
vanadium osinate in a long series of organic compounds. They found that the reddish
colour is given only with alcohols. These authors report a sensitivity limit of x.5%-
2.50/Oalcohol in a mixture of organic solvents and 2.5o/o-5o/Oalcohol, when testing
an aqueous solution.

‘Amt. Claim. Ada, 25 (1961) 85-89

,/
86 M. STILLER

If the aqueous phase (pu 3.5-5) contains insufficient alcohol together with the
precipitate of vanadium oxinate, two colours are observed on extraction in the
benzene layer:
I. the reddish colour of the alcoholic vanadium-oxinate complex.
2, the grcy-black colour of the excess vanadium osinate.
If it were possible to eliminate the vanadium-oxinate complex (I) from the organic
phase leaving only the complex (II), a quantitative determination of small amounts
of alcohol would bc feasible. Such a method is dcscribcd’hero.
When the organic coloured layers arc washed with N sodium hydroxide solution,
the vanaclium oxinate is transferred to the aqueous phase, while the alcohol complex
remains in the organic phase along with part of the excess osinc.

Determination of the absorption of the alcohol complex in benzene solution at

various wavelengths was carried out at a concentration of x.8 mmole of alcohol;
methyl, ethyl, butyl and amyl alcohols were tested (see Fig, I). In these experiments
only one benzene extraction was done. Similar curves were obtained for the four
alcohols. The highest absorption was obtained with amyl alcohol; absorption dc-
creased through butyl and ethyl to methyl alcohol. In all four spectra two flat areas
(plateaux) were found in the two regions, 370-400 m/l and 450-480 ml!.
In Fig. x, it is difficult to see the flattened areas of the methyl alcohol complex

Fig. I. Absorption of alcol~olic vanadium-oxinatc complcxcs ns function of wave-length (Bcckmann

DU spcctrophotomctcr). o nmyl alcohol complex ; @ butyl alcuhol complex: a ethyl alcohol
cc)mplcx; @ methyl irlcohol complex ; #J without alcohol.
 SPECTROPHOTOIlETRY OF SMALL ASIOUSTS OF ALCOHOLS
87

but when &e above experiment was repeated with large quantities of methyl alcohol
the curve was the same as for the other alcohols.
A control containing all the reagents used, but no alcohol, was also examined.
The spectrum of the control is apparently ‘given by osine (which is present in
excess) and which remains partly soluble in benzene even after the estraction of the
vanadium oxinate tvith alkali from the organic phase. The spectrum found for the
control has the same features as that found by MOELLERO for osine (see 4 in Fig. I).
It can be seen that the first flat area of the spectrum is an area of masimum absorp-
tion for the vanadium-osinate-nlcoholate comples. For quantitative determinations
therefore, a wavelength of 390 rnjr was chosen. At this wavelength, sensitivity is
highest and the influence of osine on the readings very small.

(I) Solution of ammonium vanadate containing I mg of vanadium per ml.

(2) 2.5% solution of 8-hydrosy-quinoline in 6;% acetic acid.
(3) 13uffer SdUtiOn of acetic acid-Sodiunl acetate, pH = 4 (100 td of acetic acid
and 53.5 g of sodium acetate).
(4) Rcnzene, 13aker analytic%1 reagent.
The two phases were kept at fised relative volumes, the ratio of the organic to
aclucous phase being z : I.

Procedwe
I ml of ammonium vnnadate solution and I ml of the oxinc solution were added to
the sample under test (containing so-500 llg of alcohol) followed by buffer solution
to a volume of 7 ml.
The mixture was shaken in a Burrcll wrist action shaker with 15 ml benzene for
20 min. After separation of the phases, extraction from the aqueous phase was re-
peated twice with fresh quantities of benzene ancl the other reagents.
The benzene extracts were collected and, after washing with IO ml of A; sodium
hyclroside solution, the optical density was read in the spectrophotometer; a Coleman
universal spcctrophotometer or a Rcckman 11U quartz spcctrophotometer was used.

Fig. z shows the relationship between the concentrations of four different alcohols
in the benzene solution ant1 the optical density of the comples at 3go m/t after correc-
tion for the blank. As might lx surmised from Fig. I, the sensitivity incrcascs with
the molecular weight. The masimum deviation in results is --_1: 2.5%. The relative
mean deviation is usually 2’vo. The smallest quantities of alcohol whicll could bc
detected are shown in Table 1.

- .-.. .-..--.-.. . - . . . ..-. ._ ..___.-_---t.. --_. .- ._-.-_-_-___ ___.___ _

Cotrrrttl ml &Ott in Cuttccnlroliott i8r
thr fip#al borrrtw the origimal samplr,
solution. lrg/ml Pglml

Duty1 or amyl alcohol 1 10

Ethyl or methyl alcohol 2-3 20-30
: -,,. ,., ,.

‘A,naC4him~.: Acta, #is.,(tbdr ) 8+8g

 The proportionality of optical density to concentration was checked up to a con-
centration of 16-20 lug of alcohol per ml of the final benzene sotution (see Fig. 2).
From Fig. z it also appears that the sensitivity of the amyl alcohol complex is
less than that of the butyl alcohol. If the amounts of alcohol are calculated in mmoles

Q2 a3 0.4 a.5 0.6

 SI’ISCTHOPHOTOhIETRY- OF SMALL AMOUNTS 01’ ALCOHOLS 89

at the same optical density of 0.15, for example, the curve for the amyl complex
appears higher than that for the butyl comples.
This is clearly seen in Fig. 3 where curves are given of optical density as a function
of molar concentration of alcohol. ”
In Table II, some physical constants of the alcohols arc given.
Possible cation interferences have not been studied but data collected from the
literature+8 shows that the metals extracted with osine at pH 4-5 are: Al, Bi, Cu,
Fe, In, MO, Ni, Ru(III), Pu(IV, VI), Sn(IV), Ti, V, W, 2%. Of these metals, only
copper is totally extracted at PH 14, while no aluminium or iron and probably no
molybdenum, nickel, titanium or vanadium is extracted.

I'ItVSIC:,\L
C:OSSTASTS OF ,\LCOIIOI.S

The author wisllcs to thank Dr. J. Yorx, Head of the dI2pilrttncllt, for iMlViCC ancl a.S-
sistnncc in this work.

.k\sPcctrt)l’hotolllctric method for the clctcrniin;ition of small amounts of mcl;hyl, ethyl, butyl
and a;rnyl alcohols is tlcscribccl. ‘I‘hc sensitivity of the nwthod is of the orclcr of 10 p&ml of test
scAution in the C;EX! of butvl ant1 srnvl nlcohols ant1 20-30 @ml in the C:LSCvf ethyl ancl nlcthyl
alcohols. ‘fhc molnr cxti*ictLn cocfficlcnt rises with tlic niolccular weight of the alcohol. ‘rhc nature
of the nlcoholic con~plcx iu not yet known.

Unc nibtliodc spcctropliotorn~tri(i~l~ cst propos& pour Ic dosage tics ;~lcools n&hyliquc, cithyliquc.
t>utyliquc ct amyliquc. On obscrvc quc Ic cocfficicnt d’cxtinction lllCJhkXlklirc atlglnclltc avcc II:
pi& md&ZUklirC dC I’dCCJd.

Ijcschreibung cincr spcktrophotomctrischcn Mcthodc: zur Rcstirnmung klcincr AIcngcn hlcthyl-,

.4cthyl-, Uutyl- untl ~\mylalkohol mit I-Iilfc dcs Vonatliumoxinat I<omplcxcs. 12s wurdc fcstgcstcllt,
chs clcr molckulnrc I~xtinktionskocffissicnt mit zurwhmcnclcn irlolck~ll;rrgc\r.icl~t clcs hlkohols
grijsscr wit-cl,

1 1;. FISIGL, Spa/ tests iu Ovgauic .4 rtdysis, 5th cd., l’ranslatcd by Ii. 12. O~:.sr~nrc,lZlscvicr, Amstcr-
clam, 1957.
Q P. FeIcL, Che~t~isf~y of Spirific, .%dcctivc a~rd .%esifivc Rractious, /\cxlcmic I’rcss, NCW York.
1919.
N. A. -rALVITIR, /fir&. Chon., 25 (1953) GOJ.
M. BORRI~L AND R. I'ARIS, Artal. C/rim. Ada, 4 (1050) 280.
1:. BUSCARONS UUEDA,J. I,.MARIN MALUMI%RI:S AND J.CLAVER.. dmd. Clriw. Artfc, 3 (15)49) 310.
T. hlOELLDR, Ilid. Bug. ~h?tll., /f tld. Bd., 15 (1943) 364,
G. H. MORRISON AND H. FRGISER, Solvml Ih-tractiotr in ,4nalylicaZ Chetnistvy, Wiley. New York,

1957,
x R. G. IV. HOLLINGSIIEAD, Osiuc am2 its Devivnlivcs, Buttcrworths, London, 1958.

AnaZ. Cllinr. Acta, 25 (1961) 85-89