Molybdenum Blue Reaction

DONALD F. CL.iUSEN1 AND JOHN H. SHROYER, Bradley University, Peoria, 111.

Areas of decreased density producing dips in the density-concentration curves

made with molybdenum blue may be found and are reproducible about 50% of
the time. Such dips take place at all points of the molybdenum blue spectra
between 400 and 800 mp; they are not associated with color changes. Under
the conditions of these experiments the dips appear above 0.14 mg. of phosphorus
(in 100.0 ml. of solution), but are not associated with specific changes in redox
potential. The dip phenomenon represents a possible source of error when the
molybdenum blue reaction is used for the determination of phosphorus with
chlorostannous acid as the reducing reagent.

T HE molybdenum blue reaction has been used for routine

colorimetric determinations of phosphorus, molybdenum,
silicon, and other constituents in a ~ i d evariety of materials.
them exhibited the dip phenomenon; these results were in-
dependent of the worker or the laboratory. In every case the
dips took place a t the same place on the density-concentration
However, in spite of its importance, the mechanism of the reaction curve. Simultaneously 1% ith the density determinations on some
and the structure of molybdenum blue are not well understood of the curves, the p I l and redox potentials of the solutions were
The equilibrium characteristics of the reaction (2) have been stud- obtained to ascertain whether or not the dips were associated
ied and the colloidal character of the molybdenum blue (6) has with changes in redox potential. The pH determinations were
been established. The average valence of molybdenum in molyb- made in the event pH variations might require that the redox
denum blue appears to be about 5.67 and if reduction is carried potentials be corrected by the amount of such variation. No
further the density of the color decreases ( 8 ) and may change such corrections were necessary. Figure 1 presents a set of
from blue to green or brown (4). Lesser color variations can be typical data. The dip in the density-concentration curve over
produced by varying other conditions ( 5 ) . the range 0.14 to 0.18 mg. of phosphorus is clearly seen. The
Woods and Mellon (9),using sodium sulfite as a reducing concomitant changes in the pH and redox potential curves are
reagent, reported that the blue color of molybdenum blue when considered meaningless because they varied widely in shape
used for the determination of phosphorus follows Beer's law up to from experiment to experiment. The pH and redox potential
1.0 p.p.m. of phosphorus, above which a negative deviation determinations n-ere done on a laboratory model Beckman pH
takes place. Clausen ( I ) , using chlorostannous acid as a reducing meter. The density data were obtained for the most part from a
reagent, reported that the density-concentration curve obtained Coleman Universal spectrophotometer and partly from a Leitz
when the molybdenum blue reaction is used for the determination photoelectric colorimeter.
of phosphorus is not a straight line but a curve and that a t a point
above 0.14 mg. of phosphorus (in 100.0 nil. of solution) an area of
decreased density may take place, producing a dip in the curve. 'Ih3'

This phenomenon is almost without parallel, although Lundberg E

(9) has observed a similar behavior when 2,6-dichlorobenxenone- -80. 1.2-
indophenol is reduced with various reducing agents. -90-
The present investigation was undertaken to ascertain whether -100. 1.1- E -
or not the dip phenomenon is reproducible and is associated with 0.7. -110.
a change in color or a decrease in density of a fixed color, and to 0.6.
attempt to correlate the dip phenomenon with changes in redm 0.5'
potential and pH. 0.4-

EXPERIMENTAL 0.3'
0.2.
In the first series of experiments a number of density-conceri-
' '
0.1.
tration curves were made under varying conditions in an attempt
to demonstrate that the dip phenomenon actually existed.
OJ '.
0
.
0.04 0.08 0.12 0.16 0.20 0.24
MILLIGRAMS PHOSPHORUS
The method used was that of Todd and Sanford (7) with chloro-
stannous acid as the reducing agent for the determination of phos- Figure 1. Inflection Point or Dip in Molyb-
phorus in blood filtrates. Amounts of from 0.02 to 0.22 mg. of denum Blue Color of Density-Concentration
phosphorus, as potassium dihydrogen phosphate, in 6.0 ml. of 97? Curve from Phosphorus Determination
aqueous trichloroacetic acid solution, were used for the curves. Changes in pH and redox potential are not significant.
To each of these were added 2.0 ml. of a reagent composed of All points represent volume of 100 m l .
equal amounts of 7.5% sodium molybdate and 10 4 sulfuric acid
and 2.0 mi. of a reagent made by dilution of a 60% solution of
stannous chloride in concentrated hydrochloric acid to 400 vol- T o ascertain whether or not the dip phenomenon existed only
umes with water. The blue color produced is stable after about a t the absorption maximum of molybdenum blue, absorption
5 minutes, at which time the solution is diluted to 100.0 ml. with
water. curves were obtained from a series of solutions of molybdenum
blue made from varying amounts of phosphorus (Figure 2).
A large number of curves were obtained by three workers in The color was allowed to stand for 5.0 niinutes before the density
two widely separated laboratories, using several batches of fresh determinations were niade. The proximity of the curve r e p
reagents. All curves produced 'IT ere nonlinear and about half of resenting 0.14 mg. of phosphorus to that representing 0.18
Preaent address. Department of Surgery, University of hllnnesota. Mm- mg. of phosphorus clearly indicates that the dip phenomenon
neapolia, Minn. exists over all parts of the absorption curve. The points at 710
925
926 ANALYTICAL CHEMISTRY

mp (the absorption maximum) from each curve were plotted

as a density-concentration curve on the same graph, using the
concentration abscissas a t the top. The resulting dotted line
again shows the dip phenomenon.

MILLIGRAMS PHOSPHORUS A T 710 M M U

0.02 0.06 0.10 0.14 0.18 0.22 0.26

D
0.9
0.5-
G 0 . 2 2 MGM P 0.E
f-0.18 M G M P 0:
60.14 MGM P
0,f
O.!
-COO6 MGM P
O.d

0.2
0.i
0 I 2 3 4 5 6 7 8 9 1011 I 2 1 3 W I 5 1 6
0.1.
TIME I N MINUTES
I

'0 .
503 550 600 650 700 750 800
Figure 3. Development of 5Iolybdenum Blue Color
Relation between density and redox potential as color develops
WAVELENGTH IN MMU
Figure 2. Absorption Curves of RIolybdenum Blue
Color from Phosphorus Determination Showing Dip from the fact that the phosphomolybdic complex before reduction
Phenomenon to molybdenum blue absorbs strongly in the near ultraviolet
Dotted line represents points at 710 m+ from each curve plotted region.
against concentration abscissas at top
ACKNOWLEDGMENT

Because it is necessary to allow solutions of molybdenum blue Thanks are due E. J. Meehan, professor of analytical chemistry,
to stand for a few minutes for color development, it was of interest University of Minnesota, for valuable suggestions and to Theresa
to ascertain the nature of this development and to trace the path Somers and Minnie Finn for their excellent technical assistance.
followed by the redox potential during this period. Accordingly,
LITERATURE CITED
samples containing 0.12 mg. of phosphorus each in 6.0 ml. of
trichloroacetic acid were treated with reagents and allowed to (1) Clausen, D. F., paper delivered before Conference of Medical
stand varying lengths of time from 0 to 190 hours. They were Technologist,s, Tri-Stat,e Hospital Assembly, Chicago, May 6,
1947.
then diluted to 100.0 ml. n-ith distilled water as usual and pH, (2) Hein, F., Burawoy, I . , and Schwedler, H., Kolloid Z . , 74, 35
redox potential, and density were obtained. Typical data show (1936).
the density dropping from 0.45 (the figure after the first 5 min- (3) Lundberg, W. O., private correspondence.
utes) to 0.36, the redox potential rising from -90 to -67 mv., (4) Munro, L. A, Proc. Trans. .\rova Scotian Inst. Sci., 16, 9 (1928).
(5) Rinne, K., Z . anal. Chem., 113, 241 (1938).
and the p H remaining approximately constant after 190 hours. (6) Shirmer, F. B., Audrieth, L. F., Gross, S. T., McClellan, D. S.,
S o explanation for the rise in E is apparent. Figure 3 shows and Seppi, L. J., J . Am. Chem. Soc., 64, 2543 (1942).
curves of this type extended from 0 to 16 minutes. As the redox (7) Todd, J. C., and Sanford, A . H., "Clinical Diagnosis by Labora-
potential becomes more negative-i.e., the molybdenum becomes tory Methods," 5'01. 9, Philadelphia, V. B . Saunders Co.,
1940.
more reduced-the density drops until, after 3 minutes, both (8) Treadwell, W.D., and Schaeppi, Y., H e h . Chim. Acta., 29, 771
curves level out. These factors suggest that the molybdenum is (1946).
reduced by degrees and that in early stages the molybdenum (9) Woods, J. T., and Mellon, M . G., IND. ENG.CHEM.,ASAL. ED.,
blue molecule contains more vibrational energy than in sub- 13, 760 (1941).
sequent stages. This explanation receives additional support RECEIWDMarch 24. 1948.

Chemical Analysis of Refinery C, Hydrocarbon Fractions

RICHARD F. ROBEY AND HERBERT K. WIESE
Standard Oil Deselopment Company, Elizabeth, N. J .

P ETROLEUM refinery distillate boiling between 4' and 51 ' C.

(39 ' and 12.1" F.) a t normal pressure is generally desig-
nated as the Cg fraction. Hydrocarbons of most common
in the production of sec-amyl alcohol, and thence methyl n-
propyl ketone and sec-amyl acetate, all important as solvents.
Tertiary Cb mono-olefins are employed in the synthesis of tert-
occurrence in this range are listed in Table I. T4e number of amylphenol, from which important chemicals and resins are
these which make up a Cs fraction varies widely, from only two, manufactured. Isoprene is consumed in the formation of Butyl
isopentane and n-pentane, in certain natural gasolines, to es- rubber and other polymeric substances. Cyclopentadiene and
sentially all in naphtha from cracking operations conducted at piperylenes also have valuable chemical and plastic derivatives.
870" C. (1600" F.) During the war a welcome supplement of high-grade motor
Recent developments have made the petroleum industry fuel was obtained by feeding isopentane and Cg mono-olefins
increasingly aware of the value of Cj hydrocarbons as chemical to alkylation units. All these processes have required adequate
raw materials. 1- and 2-pentenes comprise the starting materials hydrocarbon analytical methods in development and control.