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Masters Theses Student Theses and Dissertations

1926

A study of electrometric methods for determining selenium and

tellurium
Bertie Lee Browning

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Browning, Bertie Lee, "A study of electrometric methods for determining selenium and tellurium" (1926).
Masters Theses. 4707.
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 A STUDY OF ELECTROMETRIC METHODS FOR DETEmlINING
SELENIUM AND TELLURIUM.

BY

B. L. Browning

TJIESIS

submitted to the faculty of the

SCHOOL OF MINES AND METALLURGY OF THE UNIVERSITY OF MISSouRI
in partial fulfillment of the work required for the
Degree of

MASTER OF SCIENCE IN CH~~ICAL ENGINEERING

Rolla,![o.

1926

Approved by 7.~ t .
Associate ~rofessor of Chemistry
The2ia~ A study of ~lect~o~8tric methods
f~Jr detel.'mir.. ing sel'3:::::_~l>:'e t ..lid teJl~)J:·iu!L.
:2.rowniE~~. J.926.
 The anthor- wish.es: t· expres.s: apprecia.tion

t,o Dr.· W. T. ScllrenIc fo~' the su.ggestion of tlli.s:

research.,. and far TC;1~l.uab:le advice- and sugge·stions

gi.ven whi~e the work was in progress.
 Table of Contents

Part 1.
The electrometric determination of tellurium in the
presence of ferric iron, selenium and copper.
Introduction ••••.••••••••.•••••••••••••••••• page 1.
Tables and disoussion .•••.•••••••••••.•••••• page 3.
IJlethod and materials •••••......•...••...••.. page 7.
Summary ••••••••••••••••••••••••••••••••••••• page B.

J:Jart 2.
The electrometric determination of selenium and
tellurium by means of potassium permanganate.
Introduction •••••••.••••••••••.•••••.•.••••• page 1.
Methods of analysis ••••••••••••••••••••••••• page 4.
Titration ourve .••••••.•••••••••••••••••.••• page 5.
Tables and discussion.~ •••••.•••.•••.••••••• page 8.
Summary ••••••••••••••••••••••••••••••••••••• page 24.

Bi bliography •••••••••••••••••.•••••••••••••• page 25.

 fReprint from the Journal of the American Ch~nlic.l Society, 4at 1:.39 (1926).]

The Electrometric Determination of Tellurium

in the Presence of Ferric Iron, Selenium
and Copper

By 'w. T. Schrenk and B. L. Browning

 [Reprint from the Journal of the American Chemical Society, 48, 139 (1926).J

[CONTRIBUTION FROM THE CHEMICAL LABORATORY, MISSOURI SCHOOL OF MINES AND

MSTALLURGY]

THE ELECTROMETRIC DETERMINATION OF TELLURIUM IN

THE PRESENCE OF FERRIC IRON, SELENIUM AND COPPER
By W. T. SCHR.ENK AND B. L. BROWNING
REcsrVllD SSPTEMBER 8, 1925 PUB~ISHED JANUARY 8, 1926

The quantitative oxidation of tellurous acid to telluric acid by excess

of potassium dichromate has been shown by Lenher and Wakefield! to
be applicable to the volumetric determination of tellurium. 'The purpose
of this investigation was to study the applicability of the electrometric
method to this titration.
In converting Lenher and Wakefield's method, with slight modifications,
to an electrometric titra-tion, to avoid the use of a spot plate. indicator,
their results as a whole have been verified. The method is based on the
+ +
following reaction: 3Te02 K 2 Cr2 07 4H2S04 ~ 3H2Te04 ~S04 + +
Cr2(S04)3 + H 20, the excess of dichromate being titrated against ferrous
sulfate. It was found that selenium dioxide is not affected by potassium
dichromate under similar conditions.
Method and Materials.-Samples of pure tellurium-dioxide or aliquot
portions of a stock solution of the same material were used. The tellurium
dioxide was dissolved in a very small amount of sodium hydroxide solu-
tion, and sufficient dilute acid added to bring the final acidity to the
TABLE I
TITRATION OF TELLURIUM DIOXIDS
10-20 ce. of H2S04 (d. 1.84)
CuS04.5H20 SeOt TeOt No. of Error of Av. deviation
taken. g. taken, g. taken, g. analyses average, mg. from avo mg.
Part 1
0 0 0.2527 5 -0.14 0.18
0 0.1390 .2527 5 - .06 .10
Part 2
0 .0556 .1015-
.4023 7 .06 .20
Part 3
0 0 .2520 3 + .13 .13
0.062-0.500 0 .2520 4 .10 .10
.125 .0556 .2068 2 .15 .15
1 Lenher and Wakefield, THIs JOURNAL, 45, 1423 (1923).
140 w. T. SCHRENK AND B. L. BROWNING Vol. 48

proper value. Water was added so that in each case the volume was 200
cc. A small excess of 0.1 N potassium dichromate solution was added and
the solution allowed to stand for 45-60 minutes. The excess of dichromate
was titrated against a standard solution of ferrous iron (ferrous ammonium
sulfate), using an Eppley titration apparatus.
A ratio between the potassium dichromate and ferrous irQn solutions
was determined at the close of each day's work. The dichromate solution
was standardized against specially purified tellurium dioxide.
Part 1 of the table shows that tellurium dioxide is quantitatively oxi-
dized to, the telluric state by potassium dichromate, and that selenium
dioxide has no effect upon the determination. Selenium. dioxide in quan-
tities up to .2780 g. does not affect the titration of potassium dichromate
by .ferrous sulfate.
Part 2 indicates the accuracy of the method for various amounts of
tellurium dioxide in the presence of selenium dioxide.
Part 3 indicates that tellurium dioxide may be accurately determined
in the presence of both selenium and copper.
Summary
1. Tellurium in large or small amounts may be rapidly and accurately
determined by oxidizing with an excess of potassium dichromate and
titrating the latter electrometrically with ferrous sulfate.
2. Small amounts of selenium and copper do not interfere with the
determination.
RO~~AJ MISSOURI

•
 1'l-Ij£ :3L2~CTI~OIviETRIC DETERI\'~INATION O:B' TELLURImr Il~ THE

PRESENCE 0]' FERRIC IRON, SELENIUM, AND COPPER.

Introduction.
The quantitative oxidation of tellurious aoid
to telluric acid by potassium dichromate has been
shown by Lanher and Wakefield* to be applicable to the
volumetric determination of tellurium. The purpose of
this investigation was to study the applicability of
the electrometric method to this titration.
Hildebrana** and many others have discussed
in recent literature the applicability of oxidation
potentials to the electrometric method of titration.
G. S. Forbes and E. P. Bartlett*** demonstrated the
possibility of using the electrometric method for ti-
trating potassium dichromate with ferrous sulfate.
Eppley and Vosburgh**** showed that this titration
could be carried on successfully in hydrochloric and
sulfuric aci,d solutions. and that, the concentrations
of these acids could vary within wide limits.
* J. Am. Chern. Soo •• 45, ~423 (1923)
** J. Am. Chern. Soc •• 35,' 847 (1913)

*** J. Am. Chem. Soc •• 35, 1527 f 1913)

**** J. Am • Cham • Soo •• ' 44, 2148 (.1922)
 In converting Lenhar and 'Wakefield's method,
with slight modifications, to an electrometric titra-
tion, to avoid the use of a spot plate indicator,
their results as a whole have been verified. In addi-
tion, it was discovered that selenium dioxide or se-
lenious acid is not oxidized in sulfuric acid solution
by potassium dichromate.

rhe method is based on the following reaction:

3Te02+K2Cr207+4H2S04~3H2Te04+K2S04+CrZ{S04)3+H20

Selenium dioxide is not affected by potassium dichromate

under similar conditions.
 page 3

T'ab-le I
Titration of Te02
1.7 ae H2:S04 sp. gr. 1.84. 200 cc volume
Te02 taken 8e02 taken K2Crz0 7 used TeOa found Error
gm gm 00 gm gil

.2527 0 31.42 .2526 -.0001

.2527 0 31.40 .. 2,525 -.0002
.25'27 0 31.44 .25'28 +.0001
.2527 0 31.•40 .2525 --.0002
~2,52.7 0 31.~8 .2524 -.0003
.2.52,7 .1390 31.45 .2529 +.0002
.252.7 .1390 31.45 .2529 +.0002
.25'2.7 .1390 31.43 .25'27 .0000
.2,52,7 .1390 31.43 .252,7 .0000
.2,52,7 .139·0 31.42 .2526 --.0001

Tab1e I shows that tellurium dioxide is quan~

.
titativelY oxidized to the telluric state by potassium
dichromate in sulfurie acid solution and that the
presence of quantities of selenium dioxide up to .1Z~O

gm has no effeot upon the determination.

 page 4

Table II
Varying amounts of 8802
10 cc R2S04 sp. gr. 1.84~ 200 co volume.
8e02 taken, FeS04 required
gm oc ce
.0 20.00; 24.38
.0278 20.00 24.~O
.0555 20.00 24.37
.0836 20.00 24.39
.111,2 20.00' 24.32
.13,90 20.00' 24.44
.27'80 20.00 24.34

Table II shows that selenium dioxide is not

oxidized b~ potassium diahromate in sulfurio said of
the above coneentration. The amount of selenium diox~

ide pres,ant; up to .2780 gm. has no effeot upon the tl~

tration.
 Table III
Varying amounts of Ta02
15 cc H2S04 sp. gr. 1.84, 200 co volume
1}.1 eO 2 taken SeOZ taken 'TeOZ found. Error
gm gm gm gm
.1015 .0556 .1013 -.0002
.1521 .0556 .1521 .0000
.2018 .0556 .2020 +.0002
.2517 .0556 .2517 .0000
.3026 .0556 .3026 .0000
.3531 .0556 .3530 -.0001
.4023 .0556 .4013 -.0010

Very pure 1'602 was prepared. Varying amounts

were weighed out and determined in the presence of
8e02- The results tabulated in Table III give evidence
of the accuracy of the method for varying amounts of
Te02 in the presence of small amounts of Se02.
{a} 20 ec: H~04 sp. gr'. 1 ..84" 200 ee vol'llme

TeO 2 t:a.ken TeO' 2', f Ol~U1d Error

gm gm gm

.2.520 o .2:.52l +.QOO'1

.2520 o .2523· +.0003
.2520. o ..2.,52-0 .0000
.2520, .062:, ..2'52:'0 .0000
.2520 .125' .2520 .0000
.2.520 .250 .Z5·~9 -.0.001
.2,520 .500 .2,517 -.00:03'

{be} 1.5~ ee: RZS04 sp. U. 1 ..84~, 200 cc voltune

Te.02' taken SeOZ taken CUS04.• 5H2~ taken Te0 2 -round '~Q;r'

grrl gm. gm

...2.047 .0555 .·125," .:a044~ ~.O-OQ3

.2089 ..0550" ..125 .2089 .OO·OQ·

.01.58 gm to .1270 gIn' llave n.o e'f'fec·t upon. the determina-

tiO'Il Q'£ tell.tlrium' by t~.is metho-d. Table IV (b') indic:a.tes

tha.t telluri.um Ina¥ b·e determined ver~r aecu.ra.t.e:~y in tile

pres:e·nce Qf' small amount.s o·f bet!! s:e'lenium and copper ..

 page 7

~~THOD AND MATERIALS:-

Samples of pure ~e02 or aliquot portions of
a stock solution of the same material were .used.
The ~e02 was dissolved in a very small amount of
sodium hyd.roxide solution, and sufficient dilute
acid added to bring the final acidity to the proper
value. Water was added so that in each case the
volume was 200 cc. A sma.ll excess of NllO .K2Cr207
solution was added and the solution allowed to stana
45 minutes to one hour. The excess dichromate was
titrated with a standard solution of ferrous iron,
(ferrous BJPJIlonium sUlfate) t using an Eppley ti trat10n
appara.tus.
A ratio between the potassium dichromate and
ferrous iron solutions was determined at the close
of each day'S work. The dichromate solution was stan-
dardized on specially purified Te0 2 •
 page 8

SUMMARY:-
1. Tellurium may be determined rapidly and
aocurately electrometrically.
2. The method is accurate for both large
and small amounts of tellurium.
3. Small amounts of selenium and copper do
not interfere with the determination.
 THE ELECTROThtETRIC DETER]:!INATION OF SELE~rIUM

AND TELLURIU~~ BY IVIEMTS OF POTASSIUl[ PER~WTGL~.A.TE.

INTRODUCTION

Previous investigators have discovered that

selenious and tellurious acids may be quantitatively oxi-
dized by potassirum permanganate in aoid solution.
Brauner* reported that in the reaotion with tellurious
aoid permanganate is not rednaed to its lowest state of
valenoe. but to higher hydrated oxidase He also showed
that the reaotion is not quantitative in fairly aonoen-
trated sulfurio acid solation, due to loss of oxygen,
Gooah and Danner ** reduced the error to a negligible
figure by carefully limiting the oonoentration of Bnl-
furio aoid. Goooh and alemons*** suocessfully determ1n~
ed selenious acid by oxidation with potassium permangan-
ate.
The present investigation was to study the
electrometrio determination of both selenium and tellnr-
ium by the use of potassium permanganate. The chemioal

* Qhem.Soc. 59 .238 (1891)

**jm. lel. 44, 301 (189a)
***tm. Sci. 50,51,.(1895)
the manganese dioxide whioh precipitated was reduaed very
slowly by the ferrous sulfate. In many oases it was
doubtful whether the manganese dioxide was all reduoed at
the apparent endpoint, since a small amount remained as a
stain on the glass.
The results obtained in the first determinations
varied greatly, and the odor of chlorine was observed
during the titration. Since no hydrochloric aoid or
ohlorides were added. the question ar'ose as to the souroe
of the ahlorine. Systematic examination of the chemicals
used revealed that the sodium hydroxide which was used to
dissolve the tellurium dioxide oontained a considerable
amount of ohlorides. On adopting the procedure of dis-
solving' the tellurium dioxide directly in sulfuric acid,
the presenae of chlorides was avoided and no more d1~fi­

cnlty was experienoed from this souroe. Manganese sul.-

fate and phosphoria acid in varying amounts, both sepa-
rately and together, were added in an attempt to prevent
the aetion of the permanganate on the chlorides present.
This prooedure was unsuooessful, chlorine being liberated
as before. ~he addition of 41sodlum phosphate, and of

suffiolen~ 804ium sulfate to oonvert all of the sulfuric

aoid present to sodium acid su1fate. faile4 to prevent th
liberation of ohlorine. The conolusion was, therefore,
that the titration cO'll1d be carried out suceessfully only
in the absence of ahlorides.
It was found that the addition of phosphoric
aald or disodium phosphate prevents the precipitation of
manganese dioxide·. »isodium phosphate was used since
ita addition does not inorease the acid concentration.
On adding potassium permanganate to a selenium or tell~

urium solution oontaining disodium phosphate, the sol~

nt10n beoomes deep brown in oolor until an exoess of per-

manganate 1s present when it beoomes purple oolored.
The data obtained shows oonclusively that the
method is very accurate for the determination of either
selenium or tellurium. If both are present in the same
sample, they may be accurately determined by a combination
of the permanganate and dichromate methods.

l.m'TH ODS OF ANALYS IS -

The fo11owing prooedure for the determination

of either selenium or tel1urinm was used and is recommend-
ed. A sample containing from .14 to .20 sa. of the'Gx1de
1s weighed and dissolved in 25 00 of 4~ sulfurio aoid.
In the case of tel:Lur1UJD dl xii. t the sample must be .arm-
• ~tl1 solatiQD 1s complete. The solution is iil-tel
'reactions involved are as follows:
KgMn208~5Se02+3R2S04+2H20~K2S0,+2MnS0
4+5E 2 Se04
KZMn208+5Te02+3H2S04+2R20~ K2S04+2MnS04+5K2!e04

The reactions are oomplete in a short time, and

manganese dioxide preoipitates. The precipitation of
manganese dioxide necessitates the addition of an excess
of potassium permanganata, the excess being destroyed by
a reducing agent. Gooch and @lemons added an exoess of
standard oxalic aaid solution and then titrated the 8X-
cess with standard permanganate solution.
In the electrometric method, the exoess of po~

tassium permanganate was titrated with ferrous salfate

solution. The ohange in potential is moat marked when
passing from oxidation to reduction potential. A ti-
tration Ollrvs between po,tass1um permang'snate and ferrous
sulfate was determined. The setting of the potentio~

meter at the steepest port~on of the ourve indicates the

greatest ohange of potential with the addition of ferrous
sulfate, and was taken as the endpoint of the titration
in subsequent determinations.
!he investigation showed that two difficultie8
must be overoom.e. !he permanganate reaated with hydro-
chloric aoid or ohlorides present during titration, and

--2-
 to 150 CC 9 and 12 gm of disodium phosphate added. A
standara solution of potassium permanganate is added to
about 10 co in ex.cess. and the solution allowed to sta.nd
10-30 minutes. The excess of permanganate is then
titrated eleotrometrically with ferrous sulfate solution.
If selenium and tellurium are to be determined
in the same sample, two methods are available.
(1). The tellurium m~v be determined by oxidizing
with an excess of potassium dichromate, the excess of
diohromate being titrated eleatrometrioally with ferrous
Bulphate by the method of Sohrenk and Browning*. An

excess of potassium permanganate is then added, and the

selenium determined.
(2). The selenium and tellurium may be determined
together by oxidation with potassium permanganate. ~he

tellurium is then determined on a separate portion by

the use of potassium dichromate, and the selenium found
by differenoe.

*Am. Ohem. So. 48, 139 (1926).

Figure I.
This curve shows the change in potential
obtained on titrating potassium pennanganate with
ferrous sulfate in sulfuric acid solution.

-,-
 TABLE" I

Titration ourve o:f FeS0 a.nd KMn0

4 4

00 FeS04 Potentiometer reading

o 148.4
5 148.3
10 148.3
15 148.3
20 148.3
25 148.0
30 148.1
35 148.5
40 148.0
41 147.4
42 146.8
43 146.2
43.2 1~6.8
43.3 11'7.6
43.4 112.4
44 108.0
45 102.4
46 99.0
48 9'7.8

Table I shows the titra.tion of 30 co of perman..

ganate solution by ferrous Bulfate solution.
 ~ABLE II

Gravimetrio analysis of 8902 and fe0

2

8e0 taken 5e found SeO found SeQ found

gm 2 gm ~ 2
gm 2(oalo)
1. .2rt75 .1959 .2750 99.10
2. .2'175 .1959 .2150· 99.10
3 • • 2'175 .1961 .2753 99.21
average purity 99.14%

TeO
2
TeO
gm 2
taken Te found TeO found
gm 2( oalc}
ieo2 found
gm
'I • • 2490 .1993 .2493 100.12
2. .2473 .1973 .2468 99.'19
3 • • 2502 .1996 .249'1 99.80
4 • • 2489 .1982 .24'78 99.66

aver age pur i ty 99.8~

!he S8Q
and Te0 used were analysed gravimet-
2 2
rioally by the method of Lenherand Kao* with the
~esult. shown in Table II.

* • Chem. oa. 47. ?69, (1925)

 Table III.

Time reaction of Se02 and Te02

J?a.rt (a)-

Time Se02 taken KMn04 used Se02 found erl"or

min .. gm cc gm gm

l. 5 .1372 23 .. 6~ .J.368 --.0004

2. 10 .1372 23.60 .1:367 -.0005
3. 15 .~~72 23.64 .13'70 -.0002
4. 20 .~372 23.65 .].370 -.0002
5. 25 .13?2 23.66 .1371 -.0001

Part (b)-

Time Te02 tal'Cen KMn04 used Te,02 found av. dey.

lnila. cc cc gm from avg.
1.. 5 75 2.8.oa .2329 -.0001
2. 10 75 28.0'1 .2328 -.0002.
3. 15 75 . 28.09 .2330· .OOOC
4.. 20 75 28.10 .2331 +.0001
5.. 25 7'5 28.~2 .2332 +.0002

Tab1e III shows tha t the oxida ti.on is cOIrij?~ete

within five minutes.

 Table IV
Influence of Na~04

1~a·2HP04 Se02 precip- KMn°4 Se02 error

taken itate used found
gm gIn co gin. gIn

l. 1 .~400 yes 25.52 .~~97 --.0003

2. 2· .~4.00 yes· 25.56 .~3·99 -.0001
3. 4. .1.400· yes 25.6~ .1402 ~.OOO2
4. 8 .1400 none 25.64. .1404 +.0004
5. ~2 .].400 nOlle 25.66 .1405 +-.0005

The inf~uence of the amount of disodium phos-·

phate present is shown in table IV. In genera~~ it may
be s.tated that 12 gm. of l~a2HP04 in 200 ce of solution will

prevent the precipitation of manganes.e dioxide formed by

the reduction of 25 ee, of N/l.O permanganate for at period

of one hour. The amount necessary to prevent precipi-

tatiQn increases viith the time of standing and wi th the
amount of permanganate reduced •

....1.1..
 Tab~e V

L'1.f~uenc.e of K 2 SO'4
SeQ 2 H2 S0 KMnO',4 SeQ 2 error
taken a.dde~ used :found
gm cc cc gm gIn

~. .l4.Ql 1 25.60. .~40~ .0000

2. .1.401 3 25.6~ .1402 ~.OOO~
3'. .1.401 8. 25.64. .1404 +.0003
4.• .~401 ~4 25.67 .1405 '+.0004
5. .J..401 20 25.74. ..1409 +.0008

The ~imits wi thin which the co'ncentration of the

sulfuric acid may vary without impairing the accuracy
of the determination are indicated in tab1e V: Thia
sho~vs that the ti tration may be successful~y carried
out in, concentrations of sulfuric acid of from .9% to
1.3% by we·ight (.5% to· 7% by vo~ume).
 Tab:le· VI
Ratio of Na~04 and H2 SO 4

SeQ2 Na2HPO'4 H2SO 4 KYn<J 4 se02 error'

taken used found
gm. gm cc· ce gm gm
1. .1.378. 6 1.0 .1315
2. ..~37a 25.35 -.0003
6 15 25.34. .1.374 .... 0004
3. .l378 6 20 25.45 .. 1~80 +-.0002
4. .~378 6 25 .~38:l +.0003
5. .~378 25.46
~1. ~O 25.29 .1372 -.0006
6. .1.378 l~ l5 25.33 .l374 --.0004
7. .~3~7.8 11
8.• .
9. .1378
3'78. l~
2.0
25
25.42
25.49
.1379
.1382
+-.000l.
+.0004
~6 lO 25.33 .J.3'14 -.0004
10" .13'18 l6 l5 25.36 .J.375 -.0003
ll. .~378 l6 20 .137rz ... 0001
12. 25.39
..~378 ~6
1.3~
25 25.44 .1380 +.0002
.1.378 2l. lO 25.30 .1.372 -.0006·
~4. ..~378 2l l~) 25.35 .13'75 ... 0003
15. .~378 21 20· .1.380 +.0002
16. 25.45
.~378 2l. 25 .~385 +-.0007
25.54

Table VI shows tha,t the ratio of disodium phosphate

to sulfuric acid was found to be without effect. within
the limits of acid concentration described above.
 Table VII
Influence of excess of YJm0 4
Se02 ' KMnO& EMn04 seOZ error
taken adcte used
gm co co gm gIn

1. .1371 Z4.94 25.20 .1367 - •. 0004

2• •1371 34.94 25.22 .1368 - .0003
3. .1371 34.94 25.18 .1366 - .0005
4. .1371 34.94 25.18 .1366 -.0005
5. .1371 39.93 25.25 .1369 -.0002
6. .1371 40.93 25.19 .1366· -.0005
7. ~1371 39.93 25.20 .1367 -.0004
8. .1371 39.93 25.22 .1368 -.OOO~
9. .1371 49.91 25.27 .1370 -.0001
10. .1371 49.91 25.29 .1371 .0000
11. .1371 49.91 25.27' .1370 -.0001
12. .1371 49.91 25.32 .1373 +.0002

Table VII shows the influence of the amount

of excess of potassium per~Bnganate added. The amount
of excess present can vary from 40 to lOO~ of tha a-
rrtount used. without influencing the results of the ti-
tration.

-14-
 Ti tra:tion. of SeOa.

S'e()2 taken. IQ1n04 uaecl Se02 found Err~r'

gnl ce gm gm

Par"t fa}
1.. .J~3?6 25~~ ..26: ..1.377 +..,0001-
2. ..l~76·· 2,5 ..2,5 ...1-3.';6;. ...0000
S. ..1376' 2.5 ...2-5 ..1.376 .0'000.'
4.. ...1.376 25 ..25 .IZ~rz6' .000..0·
Far··t, (b)

5. 0-1375 2.5.34 .l~?4 -.ooo·!-

6.. .1.3'75' 25.32.. ...13,73 - ..0.00'2
'1.. ..·~374 25 ...3,~ ... 1.~7~ ~.QQO'2,
8., ..I375 25 ..3l ~1.::;~:3~ -.0001
S. .lS75 25~.~4. ..1.3'74.

F'art {el

10 • •1375' Z5'.32, ~1.374 ~.ooo·~

11.••.1.3'75 2~5.2,9 ..1372 .....0.00.;;:
12• •13"75, 2,5.2'1 ..l3?1. .... O·004~

Tab.le VIrr re~o:r·d.s:, a. t J"1'ical. dat.a.. sheet. Qf" a

seriea o·f' d..e "terrr.Linatio.na b~"- tIli.S: me',tl1o,d. and. in.dicat.••

..15-
 Titr&i.,i.an of TeOZ

TeOz. taken Kllh04 us'ed Te.OZ :round.. Error

gm cc gm gm

1.. ~:L9'al., 26.(1(1: .2QSS ~..OQ'52

2-.. ..197rz: 25'.9"Z .2028 "'-.005,1
3. .1983 2.,5: ..9:'1. .2026' ....{),04$
4. •.1.9·7.4- 25~65 ..2000: -f-.OOS2.
5. ..~9!'l~ 2.5.. SO· .1994 T.OOZl
6. '..19:75 25~ ..6Z .2004 +.002.9
? .1.986 25.6,8 .2008 +... 002.2,
8. .. I9~'13 25 .. 6~ .2003 +.oo~o
9 .. ..1.99:7 2.5 ..'1'6:, .2.0I~4, -r:.0017
10 • • 1.984. 2:5" .. 54 ~1997 +..aC.13
1, • • 2.0,02 2,5.?9 ~2~O,17' +.OO;~5·
12.... .1.9.90 2.5 ..6-3 .200,4: +.. 0014
13. ..19,82, 2.5.54 ..2Q06: +.0024
14-:. .1-98& 25 ..6"6: ..2JQQ'l +.002:5

Tah1e lX records a. series' of' deternlinat,io·ns of

~e()~ in which chlorides: I'er·e known t,o b,e present and the

Q:dar o-f escap'i.n.g' free ef'.ll.orine was no,ticed. The 'Varianee

in re-sults obta.ined. YlaJ3 therefore t.o be EaI1ec"tec..

 Table X
Ti.trati.o.n of Te0 2
TeO:2 taken KMn° 4 used Te02 fecund erl"or
gm C.C gm gm
Pa,rt ('a}
~. ..19.87 25.60 .l992 +.0005
2. .1988 25 .. 62 .1.994 +.0006
3. .1987 25.59 .1992 +.000·5
4. .1990 25.62 .199~. +-.0004..
5~. .~990 25.64 .~996 +-.0006'
6. .1987 25.57 .1.990 +.OOO~
'1. .1.993 2.5.59 .i992 .... OOO~
8. .1989 25.53 .1987 ~.OOO2
9. .1983 25.42 .1978 ... 0005
10. .1998 25.69 .~999 +.OOO~
11. .1989 25.58 ..199~ +-.0002
12. .1989 25.55 .1989 .0000
1:5. .1984 25.51. .1986 +.,0002
1.4. .1984 25.50 .1985 .....0001

PaJ!t (b )

1.5. .1984. 25.36 .1983 .... OOO~

16:. .1984 25.36 .1983 -.0001,
1'7. .1984- 25.S5 .1.982 -.0002
18. .1984 25.35 .1982 --.0002

The resul ta· l.isted in table X sho,w the accuracy

of tlle method for tel~urium in ti trati,o.ns in which.
chlorides are known to be absent.
 Tab1e XI

Ti tra tio·n of varying amounts of TeO'2

Te02 talc.en KMn° 4 used Te02 found error

gm cc gin gm

1. .0052 .69 .0054 +-.0002

2. .. O~96 2.56 .O~99 +.0003
3. .050'4 6.58 .0512 +.0008
4. .1006: ~2.95 .1007 +.OOO~
5. .2,000 25.76 • 2004 +'.0004.
6. .2997 38.52 .2997 .0000
7. .3994. 51,.3~. .3994 .0000

Tab~.e XI shows the· ac·c.uracy of the method :Cor

varying amounts of Te.02t. from .0050 gm to .4000 gm..

 Tabl.e X.II

Titration D·f SeO'2 and TeO'2

Part (a )
Te.02 Se02 KMnO'4 Te.02 error
taken taken used found
g.m gm cc gm gm

1. .O~OO .1.375 26.70 .O~O5 +.0005

2. .0696 .~375 34.38 .0702 +.0006
3. .1.501. .1375 44.55 .~494. -.000'1
4. .2.002 .~.S75 51.02 .~997 -.0005
5. .2509 .~:575 57.04. .2l1.9 -.0300

Part (b: )
Te02 Se.02 KMh04 SeO'2 erro.r
taken taken used found
gm gm cc gIn gIn

6. .1997 .0055 26.90 .0064 .... 0009

7'. .. 2002 .0269 30.66 .0265 -.0004
8. .2007 .0545 35.83 .0542- -.0003
9. .1991 .0814. 40.60 .0910 -.0004
~O. .l983 .1,091 45.59 ..108? -.0004

~1.9 ..
 In ord.er to determine whether the method could
be applie.d to the determination of varying amounts of
se~enium and te~lurium together, the data shown in
tab~e XII \vas determined.. The results were calcu1a-
ted as fol~ows: In part (al a constant amount of se-
~cnium was added, the amount of perr.aanganate required
for i t calculated from the standa,rdiza tion. and the re ..
mainder of the potassium permanganate used to calculate
the tel~urium found. In part (b} a constan t amount of
tel~urium was added, the amount of permanganate re-
quired for it calculated from the standardization. and
the remainder of the potassium permanganate used to
calculate the selenium found. Tl1e a.ccuracy of this
procedure is sho~vn by the results recorded.
-21-
 In order to find whether selenium and tellur-
ium could be determined in the same sample, the data
of table XIII was taken. ~he selenium and tellurium
were oxidized together by potassium permanganata. the
tellurium determined in a separate sample by potassium
dichromate, and the amount of permanganate required by
the tellurium in the first case calculated. The amount
of permanganate remaining was used to oalculate the se-
lenium found. This procedure is shown to be qUite ac-
curate for the determination of selenium, and the a-
mount of tellurium may be readily determined from the
dichromate titration.

-22-
 Tabl.e XIV

!itratioD. o~ Te02. and SeOa: with K2~ra97'"

then wi t.h KMn07.
T'e(l2 taken Se02.' -t·aken. DJ104 used. Se02,: :round hro-r
gm grll ec gm wn
1.. ..0701. .13'74. ~·.50' .I3'l9 ".0005
2:.. ..O:?·O~ ..~;3·'l4 23 ..'78 .};5·77 ~,..0003
~.. .0701 .1374 23.'13 .13?fi +.. 0001

In a mixtur'e' whi,ch c~on t,ai.ns both s'ele,nium and.

t.el.ltlr:ium~ the t.eI.luritml madi be oxi.dized. t-o the tellur'ie

sta.te by pota.s:s.i:l..1m di..c ·bromate and. the· excess. of the la.t.ter

de:s.troyed, by el,eetrome·tri.e titrat,ion with f'erroua B'tb1fa..t.e.
Tl-re s-e'l.eni-um. mq- b'e then determined by oxidat,ion with

pQ,tassium permanganate in the usual mann~er;. rypieel.

re·mtl'ts"; are shown in tabIe XIV.

-2Z-
SUMlvlARY: -

(1). Selenious and tellurious acids may be

very accurately determined by oxidation with potassium
permanganate and titration of the excess of the latter
electrometrically with ferrous sulfate solution.
\2). Chlorides must be absent.
(3). 1he addition of disodium phosphate pre-
vents the precipitation of manganese dioxide.
(4). Selen.ions and tellurious acids in the
same samples may be determined by using a combination
of the dichroma~e and permanganate methods.

-24-
 Bi bliography

1. Potentiometric Titrations. Kolthoff and Furman.

Wiley. (1926).

2. The volumetric determination of tellurium by

the dichromate method. Lenher and rrfakefield. J. Am.
Chern. Soo. 45,1423, (1923).

3. The electrometric titration of dichromate with

ferrous sulfate. Eppley and Vosburgh. J. Am. Chem.
Soc. 44~ 2148, (1922).

4. Some applications of the hydrogen electrode in

. analysis, research and teaching. Hildebrand. J. Am.
Chem. Soc. 35, 847, (1913).

5. The increase in oxidizing potential of the di-

chromate ion on platinum caused by certain reducing
agents. An improved method for the electrometria ti-
tration of ferrous salts. Forbes and Bartlett. J.
Am. Chem. Soc. 35, 1527, (1913).

6. Volumetric estimation of telluriu~. Brauner. J.

Am. Cham. Soc. 59, 2~8, (1891).

-25-
7. On certain points in the interaction of po~

tassium permanganate and sulfuric acid. Goo-ch

a.rld Danner. .An1 .. J. Sci. 44~ 301. .. (1.892.).

8~ The separation. of seleni um and tellurium.

Lenher and Kao. J. Am. Chem. Soc. 47, 769 a (~925).

9. The determination of selenious acid by potassium

permanganate.. Gooch and C·~emons. .Am •. J" .. Sci 50,

5~. (1895).

~o. The electrometric determination of tellurium

in the presence of ferri.c iron. se~enium and copper ..
Schrenk and Browning .. J. Am. Chem. Soc .. 48. 139,
(192.6 ).

-25-