A STUDY OF THE HETEROGENEOUS EQUILIBRIA OF SOME AQUEOUS TERNARY AND QUATERNARY SYSTEMS INVOLVING THALLOUS-SULFATE

127 Pages·04.564 MB·English

by  FISCHER, JACK

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Xerox University Microfilms
300 North Zeeb Road
Ann Arbor, Michigan 48106
LD3907 1 * - W p Z 3 3
19E>0 Fischer, Jack, 1920-
p£ A study of the heterogeneous equi-
0 libria of some aqueous ternary and
quaternary systems involving th a llo u
sulfate. New York, 1950c
86 typewritten leaves, diagrs.,
tables. 29cm.
Thesis (Ph.Do) - New York Univer­
sity, Graduate School, 1950.
Bibliography: p085-86.
C 57 6 56
c
Shelf List
Xerox University Microfilms, Ann Arbor, Michigan 48106
THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED.
LIBRARY OP
HEW YORi UiJIVXRSTTT
UHIV1RSITY PEIG-HTP
A Study of tho Heterogeneous Equilibria of eone
Aqueous 'Pernary and Quaternary Systems InvoiYing
Thallous Sulfate
A dissertation In tbe department of oher. ietry
submitted to the faoulty of the Graduate School
of Arts and oieaoe of He~ York University la
partial fulfillm ent of the requirements for the
degree of Doctor of Philosophy
by
Jack Fisoher
1950
3he author wishes to express his
sincere gratitude to Professor
John E. Kicci, whose thoughtful
suggestions and criticism s
enabled the work to he carried out.
a o i %<2 q
3
TABLE OF CONTENTS
Page
Introduction ................................................................................. 5
Analytical Procedure ..................................................................... 7
Electrolytic Analysis of Copper .................. 7
Iodimetric Determination of Copper............................ 8
Potent ioretric, Iodimetrio Determinetion of Copper 8
Determination of IhaUiui.i ......................... 10
Determination of S u lfate................................ 13
Reagents .............................................................. 18
C allous Sulfate Standard Salt .............. 18
Preparation of Pure Utallous Sulfate ................. 19
Copper S u lfate............................................................................ 21
Sodium, Ammonium and Potassium S u lfate................ 22
General Experimental Procedure ................ 24
^ternary System s ................................................................ 27
NagSO4- TLgSO 4-Hp 0, 25* ................................................................ 28
Na.cSO4-TL2SO4-II.2O, 45° ................................................................. 34
Tl2S04-(MH4)2S04-Be0, 25° ......................................................... 34
KCSO4-TL2SO4-H2O, 25° ....................................... 40
TL;.-S04-E2S04-Ea0, 10° 42
&2SO4-I2 SO4-E2O, 45* ................................................. 42
CUSO4- 312304-II2O, 25®............................................................ 84
4
TAHLii OP OU9 3SiKTS
Plage
CtiS04-(HE4)^S04-H-C, 25° ........................................................ 59
CUSO4-KVSO4-H2C, 25° ................................ 63
Quaternary Systems « ................... 65
Method of S tudy....................... 65
Explanation of 'llables......................... 66
OUSO4-(f®H4)j>SO4-Ti.' 304-E20, 25* ........................................ 67
CuS04-llf.S04-% SO4-U2O, 25* ............................................... 73
Summary .................... 83
s
Introduction
Systems of thallous sulfate and other sulfates were
studied with, the urpose of continuing the investigation of
systems involving univalent sulfates, and of comparing the
behavior in heterogeneous systems of thallous sulfate with
potassium, sodium, ammonium, and silver sulfates.
Hie 25* and 45° isotherms of the systeu HpS04-NapS04-
HpO were studied in order to compere this system with the
system ZigvSC^-lfesSO^HpO, studied by itioci and Simons^-.
Ihe 10*, 25* and 45* isotherna of the system K^so^-
TIpSC4-KgO were studied to determine whether or not solid
solutions fora tetv.esa potassium and thallous sulfate, in
view of the sim ilarity in else of potassium and thallous ions*
Hie system GUSO4-H pSO4-Iip0, 23* was skiaied at 25“ to
determine the solubility relations of the compound H.PSO4.
CU3O4.6H2O, vihoi© solubility at 25* was reported by Looke*-.
Hi is system is a part of both of the quaternary systems ithioh
were studied.
'Jhe quaternary syaten, CUSO4-'UpSO4- (M4)pSC^-HpO, was
studied at 25* in order to determine whether or not solid
solutions would be formed between CUSO4. (1^14)2-04.6HgO and
CUSO4. 33.gSG4.6HpO. Hi® qur si-ternary system &1SO4. HPSO4-
CUSO4.(NE^JpSC^-HpO was studied at 25* as part of this work.
6
Sim ilarly, the quaternary system, OuSO^-Hp.SO^KgSO^BgO,
was studied at 25* to determine whether or not solid solutions
would be formed between GUSO4. lip,SO4.6EgQ and GuSO4.tHpSO4.6BgO*
HlO
The quasi-ternary system CUSO4. H;>S04-UuSG4.K.gS04-/wae included
In this investigation.
7
Analytical Procedure
h leotrolytlo Anal yeea of Copper
Tha eleotrodepoeltion of copper, on a rotating platinum
cathode, was performed frcm a solution acidified with sulfuric
acid and nitrio acid, which had been boiled free of nitrogen
dioxide. The instrument used for the analysis was the Sergeant,
Slowin eleotrolytlo analyzer. Qhe analysis was oheekec using
weighed samples of electrolytic "Kchlbaum" copier, which were
dissolved in nitric acid. The recovery of the copper was 100.0$.
It was found; that when thallous ion was present in a
cuprie ion solution it interfered with the electrolytic analysis
of copper, ivhen the electrolysis was performed in an alkaline
solution a oopioue brown precipitate, which was most likely
thallic oxide, was deposited on the anode. The current, which
was 2.5 amperes at the sta rt c£ the electrolysis, fell to
0.2-0.3 amperes when the deposition on the anode appeared.
In acid solution a alight darkening of the anode, along with
marked decrease in the current, was noted. It was thus concluded
that the interference of thallous ion with the electrolysis of
oopper was due to an anodio reaction, vhich caused a polarization
of the electrode. The decrease in current markedly slowed up the
deposition of copper.
Due to the interference of thallous ion with the eleotrolytlo
deposition of copper, and also due to the low percentage of copper
8
in some of the saturated solutions which were analyzed, it
was necessary to use some other . e- ns of determining copper
in the presence of th&IIium.
Iodoaetrlo Determination of Copper
She iodo..fctric prooeuure, as described by lolthoff and
Scndell , was employed. eighed simples of the Kahlbaum copper
were dissolved in n itric acid, followed by n eu tralist ion with
NE4.OII, Five ml. of glacial acetic acid were added, followed
by the addition of excess El. The liberated iodine was titrated
with 0.1N NarSgOg solution, using starch as an indicator. A
few drops of nitrobenzene3 viort added to revent adsorption
of iodine on the precipitate of cuprous iodide. She standard
CuSO^.SE^O powder was again analyzed using the O.IN Na^SgOg
standard solution. She iurity of the CvuSC^.SHgO, as before,
was found to be 99.9',. OUSO4.5H2O.
Potent!oaetrio, lodametrio Determination of Copper
Shallivu:. interferes with the observation of the starch
iodine end point because of the yellow green preoipit:.,te due
to a 00 im.tion of 'HI and Cul. It w s thus necessary to
detect the enu point of the iodow.etric analysis potentio etrioally
using a Beckman reee- rch model G- pE meter. Platinum and calomel
electrodes ’were used as the indie , tor electrodes.
She titix tion curve for the ; otantio. etric c.n lysis is
shewn on graph I. She inflection in the curve occurs at 0.19