Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Look up keyword
Like this
1Activity
0 of .
Results for:
No results containing your search query
P. 1
Miller 1959

Miller 1959

Ratings: (0)|Views: 12 |Likes:
Published by bakasudha

More info:

Published by: bakasudha on Dec 05, 2012
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

07/30/2014

pdf

text

original

 
Reductor
Table
I.
Reduction of Thallium(lll) to Thallium(1)
KO.
f
Detns.Cadmium
5
5
7
a
Bismuth 4
4
4
4Silver432
5
T1,
Mg.
Taken Found,
av.
32.0 31.953.1 5'2.9106.4 106,3212.8 212.732.0 32.053.1 53.1106.5 106.4212.8 213.132.0 32.053.1 53.0
106.5
106.5212.8 213.1Std.Dev.0.220.330.200.40
0.10
0.170.250.390.110.100.140.44mium rod (Fisher Scientific Co.) were was added40nil. of
6-Y
hydrochloricwashed with
lil'
hydrochloric acid and acid. The thallium(1)
lyas
titratedthen with 1N sulfuric acid.potentiometrically with
0.1000A7
potas-Bismuth.The chunk metal (Fisher sci- sium bromate using the Fisher Titrim-eter with a platinum-calomel electrodentificCo.)was crushed and the coarsepieces were sorted out.Silver. Granular silver
(G.
Frederick pair*Smith Chemical Co.).Blanks were run on the reductorswith the above procedure, but substitut-The columns were washed nith
1K
ing
50
nil, of
l,oLv
ulfuric acid for thesulfuric acid and kept filled nith
0.01N
thallium solution. The correction, insulfuric acid when not in use. terms of milliliters
of
0.1s
potassiumbromate,
was
0.02
ml. for the bismuth,
0.03
ml. for the silver, and
0.05
ml. for
ROCEDURE
Measured aliquots of the standardthallium solution were treated to givesulfuric acid concentrations from
0.1
tol.O*Vand total volumes of
50
to
100
ml.
Each solution was uassed through thethe cadmium reductor.After the blank correction was de-ducted, the results
shown
in Table
I
were obtained.
DISCUSSION
\Tit11 jo-ml. portions of
0.1N
sulfuric bismuth, cadmium,
or
silver. Theacid. To the solution and washings blank corrections for these metals are
Use
of
DinitrosaIicyIic
Acid
Reagent
for
Determination
of
Reducing Sugar
GAIL
LORENZ
MILLER
Pioneering Research Division, Quarfermasfer Research and Engineering Center, Natick, Mass.
small but may vary from lot to lot,depending
upon
the purity.The results obtained with silver com-pared favorably
n
th those obtainedaith bismuth or cadmium. Upon ad-dition of hydrochloric acid, a precipi-tate of silver chloride is obtained.
Al-
though the results do not indicate anyloss of thallium chloride by coprecipi-tation with the silver chloride, the
use
of the bismuth or cadmium reductors
is
considered more convenient. Khenbismuth or cadmium is used, thallium(1)chloride, formed upon addition of
hy-
drochloric acid, disappears
as
the titra-tion proceeds. In the ease of silver,the silver chloride remains, and there isno visible rridence that the thalliumchloride has been completely oxidized.This is not
a
criticism
of
the reductionby silver, but rather
a
limitation of thebromate method, which requires theaddition of hydrochloric acid.Other reductors studied were lead,aluminum, zinc, amalgams of zinc,cadmium, lead, and bismuth. Sone ofthese proved satisfactory. Sickel re-duced the thallium quantitatively butthe blanks nere high and erratic.
A
better grade of nickel metal nouldprobably serve satisfactorily.
LITERATURE CITED
(1) Anderson,
J.
R.
A,,
rlx.4~.
HEBI.
5,
108 (1953).(2) Zintl,
E.,
Rienacker,
G.,
2.
anorg
Chem.
153,
276 (1926).RECEIVEDor revieTY January 17, 1958.Accepted October 27, 1958.
b
Rochelle salt, normally present inthe dinitrosalicylic acid reagent forreducing sugar, interferes with theprotective action of the sulfite, but
is
essential to color stability. The
diffi-
culty may be resolved either byeliminating Rochelle salt from the rea-gent and adding it to the mixture ofreducing sugar and reagent after thecolor
is
developed, or by addingknown amounts of glucose to thesamples of reducing sugar to com-pensate for the losses sustained in thepresence
of
the Rochelle salt. Theoptimal composition of a modifieddinitrosalicylic acid reagent
is
given.
HE
DINTROSALICYLIC ACID
REAGENT,
*T
eveloped by Sumner and co-worker
(11-14
for the determinationof reducing sugar, is composed of di-nitrosalicylic acid, Rochelle salt, phenol,sodium bisulfite, and sodium hydroxide.According to the authors of the test,Rochelle salt is introduced to preventthe reagent from dissolving oxygen
(12);
phenol, to increase the amount of colorproduced and to balance the effect ofphenol encountered in urine
(IS);
andbisulfite, to stabilize the color obtainedin the prescnce of the phenol
(IS).
The alkali is required for the reducingaction of glucosc on dinitrosalicylic acid.The major defect in the test is in the
loss
of part of the reducing sugar beinganalyzed. This was pointed out bySumner
(12,
14,
was referred to byBrodersen and Ricketts
(Z),
and hasbeen observed repeatedly in this lab-oratory
(6,
8,
9).
Evidence of loss ofsugar is also given by the data of
Hos-
tettler, Borel, and Deuel
(4)
and ofBell, hlanners, and Palmer
(1).
As
this defect appears never to have beenfully remedied, the present study wascarried out to investigate the differentfactors which might cause it. In thecourse of the investigation, the effectsof varying the concentrations of the
426
ANALYTICAL CHEMISTRY
   D  o  w  n   l  o  a   d  e   d   b  y   C   A   L   I   S   C   O   N   S   O   R   T   I   A   C   H   I   N   A  o  n   J  u   l  y   2   6 ,   2   0   0   9   P  u   b   l   i  s   h  e   d  o  n   M  a  y   1 ,   2   0   0   2  o  n   h   t   t  p  :   /   /  p  u   b  s .  a  c  s .  o  r  g   |   d  o   i  :   1   0 .   1   0   2   1   /  a  c   6   0   1   4   7  a   0   3   0
 
different components of the reagent
also
were determined. The findingswhich resulted have led
to
the develop-ment
of
a
modified reagent and pro-cedure.
METHOD
The color tests were made with 3-nil.aliquots
of
reagent added to 3-ml.aliquots of glucose solution in 14-mm.tubes. The mixtures were heated
for
5
minutes in a boiling water bath andthen cooled under running tap n-ateradjusted to ambient temperature. Cool-ing to ambient temperature was madenecessary by the effect of temperatureon the absorbance
of
the colored reac-tion product
(w),
n effect confirmedby the present studies. The color in-tensities nere measured in
a
Beckmanllodel
DL
spectrophotometer at
575
nip
n
th a slit
n
dth of
0.06
mm.The reagent of Suniner and Sisler
(14)
and a modified reagent wre used inthe tests. The former contained ap-proximately
0.63Yc
dinitrodicylic acid,
18.2%
Rochelle salts,
0.57,
phenol,
0.5%
sodium biqulfitc, and
2.14%
sodium hydrouide; the modified rea-
gent
coiitained
1%
dinitrosalicylic acid,
0.2%
phenol,
0.057c
sodium sulfite,and
1%
sodium hydroxide.For certain tests the modified reagentincluded varying concentrations of
Ro-
chelle salt. The composition chosenfor the modified reagent n-as based onthe resultq of preliminary tests
n
hichindicated that such
a
reagent
was
optimal and
~ould
ene best as thebasis
of
rrference for testing effects ofvariation
111
composition. In the ab-qcnce
of
Rochelle salt, the color
ob-
tained
n
th the modified reagent
n
sunstable. To stabilize the color underthese conditions,
1
ml. of
a
40%
solutionof the salt was added to the mixture ofreactants subsequrnt to the develop-nicnt of the color and prior to cooling.The modified reagent
n
as preparedby placing all solid components in
a
container and dissolving them simul-taneously by stirring with the requiredvolume of sodium hydroxide solution.This was much simder than other mo-cedures
(3,
14).
The modified reagent produced thesame color with glucose from day today, thus proving more stable in thisrespect then the reagent of Brodersenand Ricketts
(2).
Modified reagent towhich Rochelle salt vias added also didnot change from day to day in thisrespect. Depending upon storage con-ditions, however, the modified reagenttended eventually to deteriorate fromatmospheric oxidation of the sulfitepresent. Deteriorated reagent was re-juveiiated by the addition of freshsulfite. The danger attendant uponoxidation of sulfite could be avoided bypreparing the reagent in large batcheswithout sulfite, the sulfite being added
to
aliquots just prior to the time whenthe reagent \vas to be used.
STUDY
OF
VARIABLES
Removal
of
Dissolved Oxygen.WITH
STREAM
F
KITROGEN. umner
TR€AT€D
0
0.1
0.2
0
0.30.6
fbl
0
03 06
63
0
0.3
06
IROCH.
SALTS^
I
63
0
0.3
06
fc)
0
03 06
fdJ
0
03 06
03
CITRATE
0
0.3
06
(e/
ffJ
fgl
fhl
MILLIGRAMS GLUCOSE
Figure
1.
acid reagentEffect
of
variables on color
produced
with glucose and dinitrosalicylic
a.
b.
d.
e.
f.
9.
h.
C.
andStream
of
nitrogen passed through mixture; Sumner’s reagentSodium sulfite treatment piior to addition
of
Suniner’s reagentRochelle salt concentration; modified reagentSulfite concentration; modified reagentPodium hydroxide concentration; modified reagentPhenol concentration; modified reagentDinitrosalicylic acid concentration; modified reagentCarbox) methl ]cellulose, citrate, and miitures
of
both present; modified reagentSisler
(14)
indicated that theloss
of
glucose with the dinitrosalicylicacid reagent was due to destructionby oxidation, and based their state-ment on unreported results of ex-periments in which a stream of nitro-gen was passed through the reactants.An attempt to confirm this observationin the present nork indicated thatpassing
a
stream
of
nitrogen through
a
mixture of Sumner‘s reagent and glu-cose for
2
minutes prior to the develop-ment of color largely eliminated thedestruction
of
glucose (Figure
1,
a).
WITH STLFITE.
As
sulfite had pre-viously been used successfully for re-moving dissolved oxygen from aqueoussolutions
(b),
it
was
surprising that thesulfite present in Sumner and Sisler’sreagent failed to accomplish this pur-pose. To test whether this failure of thesulfite may have been due to interfereiiceby other components of the reagent,sulfite at a level of
0.1%
n-as
added toglucose samples prior to mixing themwith the reagent. This procedure re-duced the destruction of glucose byabout
707,.
The rewlts, shown inFigure
1,
b,
thus provided strongevidence for the suspected interferenceby the other components of the reagentunder the usual conditions of the test.
INTERFEREWE
F
ROCHELLE
SALT.
Comparative tests were next carriedout with the modified dinitrosalicylicacid reagent to
M
hich varying amounts
of
Rochelle salt were added. Theresults, shorn in Figure
1,
c,
clearlyimplicated Rochelle salt
as
the majorfactor involved in the interference withthe removal of oxygen by sulfite,because, in the absence of the salt, thesulfite appeared able to remove thedissolved oxygen and thereby to pro-tect the glucose. iiside from con-tributing to the loss of a portion
of
theglucose, the Rochelle salt caused anenhancement of the color due to theremaining glucose.Sulfite Concentration. The effectof different concentrations of sulfitein the modified reagent (Figure
I,
d)
indicated that
a
maximum color in-tensity nas obtained
at
0.057,
ulfite.In experiments not shown, essentiallythe same results were obtained at
0.025
and
0.1%
sulfite as at the
0.057,
level.
Low
concentrationscaused a lack of linearity, nhileboth high and low Concentrationscaused a depression in color intensityand a
loss
of glucose.Sodium Hydroxide Concentration.The effect of different concentrations
of
sodium hydroxide is shown inFigure
1,
e.
High concentrations ofsodium hydroxide led to enhancedcolor development, but at the sametime contributed to a loss
of
glucose.The level of
1%
sodium hydroxideappeared to be the most suitable,
as
it
produced the maximum color in-
VOL. 31,
NO.
3, MARCH 1959
*
427
   D  o  w  n   l  o  a   d  e   d   b  y   C   A   L   I   S   C   O   N   S   O   R   T   I   A   C   H   I   N   A  o  n   J  u   l  y   2   6 ,   2   0   0   9   P  u   b   l   i  s   h  e   d  o  n   M  a  y   1 ,   2   0   0   2  o  n   h   t   t  p  :   /   /  p  u   b  s .  a  c  s .  o  r  g   |   d  o   i  :   1   0 .   1   0   2   1   /  a  c   6   0   1   4   7  a   0   3   0

You're Reading a Free Preview

Download
scribd
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->