A STUDY OF ZIRCONIUM HYPOPHOSPHATE

Thesis for the Dag!” of M. S.
MICHIGAN STATE COLLEGE
Ramon F. Rolf.
1954

\
x

\ $-4-
z 3099’} . .. .
\v' ab\\ch-1ij

;
l.

1‘91.

v“

‘ - ~> 9-K» ‘
4;; "3!;‘12‘1-1MW'..J... «

 

A SEUDI 0F ZL’iC OETEfi MOPEOSmeE

3y

Ramon.r. Half

A T213313

submitted to thn Schoel of Graduate Studies orifiichigan
Stat. 0911030 of Agriculture and Applied Science
in Mill fulfillmnt 01' the requirement!
for the degree at

nusmna 0? SCIENCE

Department of Chemistry

1951;

 

:1- I

Luv

» .| V tAn .530

ACKKQWLEDGHEET

Tho author wishes to express his unsure
appmntion to Dr. Elmer Miningar for his
patient guidance and prudant counsel thro’ -
out tha court. a: this work.

WW
Wit}
{til-W
ma»

*3?

Iv

gun
.5:

is
a}
if)

a}:

TABLE OF COME???

Page

mRmIm;OOODIOOIOOIOIIOOIOIOOOOOOOOOOQIIOOOOO0.00.0000...
mmflOCOOCOO0.0QQOOOOQOOOOOOOOO0.00IOOOIIIOBOOOOIO0....

Reagent- Ind Stmdu'd Solutienl..........................
Variables Involved in the Graviznatrio Hypophoaphato
Determination of Zirconim............................
Determination of Phosphorus be Zirconizm Ratio in the
Freeipit‘uOOQdo.0000...0....00.......OOOOOIOOOOOGOOI.
X‘Rq Diffrmfion 3311119. 0: mewitamo00¢occuuaooooob
comctmw ‘31 fl riu‘tiom.000000000.0.0.0...O60...

DmssmlOOOOQO;IQOIQI0.09.0100...00.0..I00...OOOOOOOOOIIOOOO

WIOOOOOOD¢OOOQOI.0000-Ono-0.009000000000000.0000000300000

mm CREDOODIOCOGODOQOQOOO...0.000.000.0000.0.0.0.9...

0‘9!”

18
20

22
2h
25

1153091101? 1%

Zirconium in dilute mid caution in reported to yield an 133-
tolublo precipimo at 21-150th upon th- addition of diaodim
dilvdrogen WWII“. (8) , 'but udditioml intonation on the
proputici at the precipitate are halting.

the pan-pan or thil investigation was to study tho nation b.-
mon SW1 ions and mmmu ions and tho propane. or the
Mpitlh in tin hapo of working m cm: mom analytic-J.
woe-dual.

Aw Quint-unit. (inclination of sitcom.“ “in: Wholphnto
would depend an 1511. mouth: of the 1M1. nympho-phat. pro-
upmu. Fruhly manna-tad thou-1n mhmhm bu been round
to max-b both humane-phat. and than: Lonl (1‘4). 2m- to the
alums; 1n thu chunk-1n o: thawin- and sis-comm it no cou-
lidu'id moan-y to Itudy tho Itomhimotry of the nation batman
linear]. and nympho-phat. ionic .

ram (17) preplrod thorium Egvpoxahoaphato by adding ¢ 10-20%
on.” of. 0.05 l! «Sundial dflvctrogan Mophosphato to u boiling solu-
tion of 0.05 H thoriun nitratc cont-dung 10$ hydrochloric «1d.
This minut- In :1: dried «to: whim with 51 Wehhru acid
and convincing to mow omen hypophaaphato. Individual ample:
of this maipiutc mo (ii-solved 1n n mixture of concentrated
mm. and Min; nitric acid and 11331de for mum-phosphoru-
ratio by precipitating tho Wu u the hydrou- oxido Ind treating

the filtroto with ammonia nolyhdo‘bo to precipitate! tho phosphoto .
Thio molyoio ohoood 1 otom of thorium to 2.203-2 .238 atoms of pines.-
photos. mm onolyood ooporoto “samples for thoriuo and phoop‘noruo
and obtainod orrotio rooulto duo to continual loos of water from the
thorim hypophoophato .'

Hoollor one! omen (14), studied thorim rmaophosphm and fomxd
' that it odoorbo mopmpmta and mm 1023 . Tho adsorption of
hypophoophoto woo {aloud by a radimmtria: “chum 1min; phoen-
pboruo-jsz .- Adoorpuon or thorim in macaw-u ooid ooluuon boo
boon round to peptixo thoriu- mophuphm to oloar oolo which can
bo :11th and thou oodhon’sod 12:1 the ultra-centrifuge. ‘rhorium hypo-
121101th In: pi‘oporod by odding mgxtly loos than tho owivolont
quoatity of di- odimo dirvdrogon hypcrphoophoto to thoriul nitr oto and
mixing tho Insulting prooipitoto ”nit-h othonol and othor. Thio pro-
oipitoto woo found to be mn-oryatollino by I-roy diffraction.
conduotmtrio titration studies or thoriuo ond bypaphoophoto hovo
ohown tho prooipitoto to be T1050”

Tho procoduro tolloood in the present work was deviaod to ohm}-
tho following:

1) Tho oomplotonou of tho precipitation of siroonim by

Weaphau.

2) Tho oompooibion of tho precipitate...

3) Tho oompooition of tho rooidno otter ignition.

h) The accuracy of tho dotominotion at zirconizm by pro.

oipiution u the hypoyhoophoto .

Tho increasing importance of zirconium until end illcye has
Itinulated interest in the de termination of zirconium. The older
methods ouch as the phosphate, cupferron, oolenite, arsenic acid,
etc. are not ontirelyloatiefactory being slow graviectric loath-ode.

The literomnre on tho determination or zirconium up to 1959 has
been covered quite conploteiy'by.Freceniue and Jaudor (h). A'bric!
economy of the contributions mince that date relieve.

Willard and Hahn (21) mprovcd the phosphate method by tuning
metaphoephote to give homegonouo precipitation of zirconium phosphate.
The ignited precipitate gave on Iqrcy pattern identical to that ob»
tained by the use of orthophoophate. An extrmely dense precipitate
on: be obteinod by means of trimcthyl phosphate, but due to the fact
that o.12-15 hour boiling period in required, this method is not
practicol.

lumino (12) node the important oboervotion that nondelie acid
procipitotoo oireoniun nondeloto from o dilute hydrochloric or cul-
furie ocid oolution, end that the precipitate can be ignited to
Iirooniun Oxide. Eafniun is the only known interference.

‘ Cooper and oo-uorkere (16), found parabrcnomondelic and para,
chloronondelic ooido to be superior to nondolio acid, Zirconium
londoloto and tirconiul porohalcnandolotee can‘bo used as weighing
tom otter drying “110°C, but the zirconimnhelomandeletee can be
washed Iith water while the zirconium nendelate must be flushed with
I 51 solution of'nondolic acid. The uee of parachlorcmandelic or

parabrcmcmandelie acid offer o.noro favorable gravinetrio rector.

Hahn {7) ho: compared.mandelic acid and orthcphosphate on pre-
cipitating reagents for ancll amounts of xirooniun, and has found the
mandolin acid method to be as accurate as the phosphate method.

Klingonborg and Popuoci (llnhave applied the holcnandelio acid
method to the determination.cf zirconium in Itcal.

Popucci and co-vwrkore (1.8) have upplicd halomndolio acids to
the determination of zirconium in aluminum alloys.

Considerable attention,has'beon given recently to the devologmant
of colorimetric cud epoctrophotometric methods of determination.
Horton (9) has proposed the use of thoron [2-(2 lvdroxy 3,6 disulfonio-
l-nephthylezo) benzene arsonic acid] as a reagent for the spectro-
photonetric determination of lirconium in the range of lOélOO ppm.
Iron, chrunium tin, uranium, molybdonum, titanium, phosphate and
fluoride ions interfere if present in too large a ratio to the zirconium.

Grtnaldi and'White (6) have dcocribod a spectrophotometric method
for the determination of Iirconi‘tm in which the zirconium il concen-
trated‘hy precipitation with paradinethylanino-azcphonylaraonic acid.
After concentration of the zirconium, qncrcetin is need an the color
devdloping reagent. This method is ocgfieeted for use in the dotcrmin-
eticn.ct 0.1 to 50 part. of xirconinn per million parts of sample.

Thaner and Voigt (23) have described I.nagenta colored complex
which is formed by zirconium and chloranilic acid in two molar
perchlcric laid. Earniun, uranium, thorium and Itannic tin giro the
ewe color a: zirconium ~ This complex may possibly be used for a

spectrophotonetric determination of zirconium

A fluormctric no nod for tho detcminaticn of zirconium he:
been reported (1). This mothod is based on the measurement of the
blue tlnorcsocnce given by xirooniuo and flavanol (3-hydroxyflavone)
in nmicrctcly atrong o'clfzu-io acid aolu'tioa, when armed to 1.11%:-
violet light. reliminarj treatment using deposition at I mercury
cathode and nrccipitation with soaiiun twig-oxide are noceoearg to re-
movc interfering 5.0M. Phocyhace am fluoride must be absent as

they quench the fluorecconce.

Enmmmmr.

Resgents and Standard Solutions

Himty-tlvo pm of disodim dillydrogon hmphosphato hexa-
wdrau m. pupa-ed by tho method or" lenlngor and Chulskl (13).
This preparation was roorystsllind Mos from water to insure high
purity. Provlous ml: in this lsborstory sud othors (3,15) has shown
thst s produot of primary standsrd node is obtained upon sir drying
tho recrystallised compound. Standard solutions of 0.05 I! disodim
dihydrogon IVpoPhosphsto ssrs proposed by dissolving 7.8511: plus in
"to: ad diluting to 500 I1.

Proporsuon or s stsndord zirconiu- solutiom sixty-ho pus
of C. 1’. 81mm]. nitrsts ddlxydrsto vss dissolvsd in appromsuly
7 lltors of rotor. Ono Imndrod ll of 6 I hydrochloric was added to
$110 unann- solution to prom hydrolysis. This solution was
tiltsrsd sitar standing 1w 3 duo sad stsndsrdissd for six-coal“
dioxido by tho nsndslio sold uthod (12) . Thros aims- at 2h.9h
s]. of slrsosms solution vars dilutsd to he :1. Ton ll of oonosnorotod
Winnie sold In! 50 ll! of 16% landslio sold tors sddod to sub
cap)... the tuporstnro was slowly rsisod to 85°C and hold thoro for
20 moss snd tho hot sssplss vars rum-«1 through io-hZ thmsn
pspsr. Tho insolubls smoulus smdolsts sss Inshod nth s hot solo-
not: condone 21 hydroohlorio sold and SS sandolio sold. The washed
wipitstos mo ommlly 1mm to zirconius dioxide and weighed.
Tho rosslts srs given in Tools I.

I

C
c
v
,.
i
.‘
O“
x
u.‘ ‘
s
o

.r‘

TABLE I
MWflOl H mm 801.3110!

_-——-‘ —A_—— __;__ A A ”A” , A A.—
A

III

 

Aliquot ' ll. of Zr fiolution arms of 21-0. For“
1 , ‘ ‘ 21.31; ‘ ' 0.11m
2 ' ‘ 2mm 0.1149
3 214 .91: A 0.11m

ivorsgo 0.11418

Tho colorless standard sirooniu solution boos-o yellow sitar tho
addition of Woohlorio said. Aoidii’iod 25 :1 susplss of tho
5mm solution sud tho 0.05 n cumm- dihydrogsn maphosphsto
solution woro ossh trsstod sit}: s dilute solution of sodium thiooysnsto .

Tho sireonius solution (as s positiss iron toot, mils the hypo-
phosphsto solution gsvo ‘s mastin test. A quantitstivo dotsminstion
of tho iron wss node by rosding tho absorbsnoy of tho torrons ortho-
phonsnthrolino «mph: on s Boom N Spootrophotouotor. Tho
siroonius solution oontsinod 0.00611 iron snd tbs disodixn dihydrogon
hypopholphats was sound to contain loso thou 0.00011 iron. Spectro-
ysphio Wis of disodius dilxydrogon maphosphsts gsvo only
sodius, pun-pm snd trsoo iron lines.

Prop-notion of s oonoontrstsd sirsorwl nitrate solution for con--
ductonotrio titrstionsa o. P. sirooqyl nitrsto (shout 50 arms) was

§.

.
--—_
“-o
.0-

 

 

s v
..
c -
c

o-

4..
n

l

H.

_. -
*H‘
l

‘ I

V“

q .
t n.
-“l’

9-

- o -. .
. ‘.- . -

—¢

dissolved in 1 liter of ureter . This so ution was stmdm-dized by

the mandolin eoid method. The roenlto or standardizstion ere given

 

 

 

in Teble II.
TABLE II
snmmmnon or 2133051025 sown/3n FOR
comummxc firmness
z: i A: A...” . A»: m f “#12::
Concentrated Zirconig Solution-’-

4 iii ”P ° _; ll __ up ' ' m ‘__
101m 4»: solution 21.32. mm
mae- zro. 0.6692 0.6681
nomioy 0.2178 0.217h

Vex-isblos Involved in the (h'svinetrio Mophosphete
Detoninetion of Zirconm
A gnslitetive study of the physics}. neture of tho sirooninn hypo-

phosphete preeipitste one node in the tanning nenner . Twenty-five
n1 or 0.95 s disodim dihydrogen wombat. m added dropiise to
ash of three 10 I1 aliquots of the standsrd sirooniue solution. The
white precipitates were bulky end geletinons‘. One precipitate was
digested 30 minutes end one use digeeted our night. There use no
opporent difference in density between the undigested sample and the
sample digested 30 minutes. The sample digested over night appeared
to be slightly less bulky.

 

u--.“

 

h-—»

A-

In order to study the completeness or the procipitstion of
sirooniun end the stoichioletry of the reaction, equel snples or
zirconium were trested in the following manner. filiqnoto of the
stmdud sirooninn solution (0,111.18 am 21-0.,5per 211.924 ml solution) were
treetsd with varying mounts of hydrochloric scid end then diluted
to 165 :1. thirty-rive e1 of 0.05 n 01-mo- ammo.” hyponhoophato
were added dropwise to each of the dilntod' samples. Thirty-five ml 0
of disodin dihydrogen lupophosphete represents s 521 excess, seem-.-
ing the eeepm toned am”... in. e-plee lore digested for
on hour end e not, treated with mm pulp, altered, wheel with
2.51 W esid eed ignited to constant weight st 2.000%.

Tb results of melyeis ere tabulated in Teble III.-

TABLE III

V 1m: Cl ACIDITI Cl PERIPITAIIOI (I mom.
DHIDROGEH HIPOPEG‘SPHATB

.— A

—- #— v—w— w w
4. ___ _._.-_ MA; Am —4 ‘fl
7" .w—V. w w—w—viw fl. ‘7— w—wyv—v— ‘

tense! Cono. of EC]. in H1. 0.05 H mm or

 

luple 31-0, Token tins]. Solution lefigfi. Added Ignited Residue
l 0.11.18 0.6 I 35 0.3096
2 0.1015 1.5 I, '35 0.3157,
3 0.11318 1.5 I 35 0.3151
h 0.1h18 2.9 I 35 0.3155
5 0.1h18 2.9 I 35 0.31914
6 0.11418 (.9 I 35’ 0.3176
7 0.1h18 5.9 I 35 0.314%
B 0M8 9.0 I 35 0.3156

Average 0.3151:

v.-
4-
..

I
-._
,

d4.

—"

 

.-

p.-

v.

 

13)

The filtrates from staples l, 2 , 11,, 7 and 8 in Table II were
sdjuetod to 10! in hyd'roohlorio mid, treated with 5-0 ml of; 165
mandolio said end hated to 85°C. All the solutions renaincd clear.
therefore, under the stated oonditiono ,‘ precipitation of zirconim
by disodilm dilvdrogen bypopbosptnte is so complete so precipitation -
by nsndelio said. '

The theorou‘icsl might oi‘ sirooni‘am pyrophoephato that could be;
obtained Ira OJJQB firms of ammonia“ oxide is 0.3051 grams. The
imition weights are too lsrzo tor the residues to be siroonixm pyro-
phosphate. This oness‘seight may be due to adsorption or occlusion
by the gelatinous precipitste. 0oolusion could be dooro need by more
thorough aching e: the precipitate or by precipitation from a more
dilute solution.

A series of half sise suples were run using the some totsl
volumes that were used for the full sise snples. these halt sise
samples were prooipitsted tron lore dilute solutions than the m1
sise ssnples and error due to occlusion and ooprecipitetion say be
reduced. The belt size suplos slso gave smaller precipitates \dlich
could be washed sore thermally. To obtain half size sesples, the
steedsrd sirooniu solution see diluted 131. this (eve e secondary
standerd siroonius solution containing 0 .0709 greens st siroonins oxide
130? 2&9}: ll of solution. .

1 series or on: me unple- (0.0709 pe— no.) were run in
the seas manner as the m1 sise saples (0.11018 grams 21-0.) . Results
of enslrses or ball-use samples are tabulated in Table 1'. these

11

half size suplos pm residue Imigfits which were high-oz- than the
theoretical Weight for ziroonims pfi‘opheng-mto. But those residue
weights are 1.7 per «at high as smpsrod to 5.1 per cent high for
the full Dayle .180.- these resume indie than that high results are
partially due to coprocipitstion by the precipitate or incomplete
trashing of the preeipitato.

TIBLE I?

my)? a? SAMPLE SIZE 021 THE PRECIPITATION or inseam.
. ' ammaoam XIPOPEOSPWA‘E

##4## A.“ _J_‘ - A n 7' A 4%

W

.L. A _. _- .__..‘_._

‘- f ~—. ,_,. if v ' .7. ‘—V‘— w

fi‘sms of Coats. of EC]. in El. 0.05 H Grams of

 

 

Simple 21-0. Token Finn solution Iofiifi. Added Ignited Residue

1 0.0709 1.5 I 18 0.1530
2 0.0709 ' 1.9 I 18 0.1560
3 0.0709 2.9 I 18 0.1653
14 0.0709 5.9 i 18 0.15?!)
5 0.9709 5.9 H 13 0.1560
6 0.0709 9.0 l 18 0.1563
7 0.0709 9.0 x 18 0.1535
8 0.0709 13.1 I 15 0.1538

Average 0.1551

A .A-. _“_4

For the only”. tsbelstsd in rsble m s 561 senses of hypo-
pho-pmu on used, seeming the precipitate to be magma”

In order to «up». the mmphm precipitsuon of sireonim
with other phosphste prooipitstions , tour sliqnots of the stsnderd
zirconium solution (0.11;.18 pm 210.) were run using lekors snag/zed
nets phosphorie soid as tho precipiteting reagent (21). the four

equal mphe of eirooniue sore eseh treated with 20 ml or concentrated
sulfurio said end diluted to 175 :1. live you or Bakers easlyssd
sets phosphorio said sore dissolved in 25 ml or enter end we sdded
to each or the "-91... The sIlples em then digested am- right,

- trotted em: tilter pulp, filtered, washed with 53 mm nitrsto

end unit-a to constant weight st 1000’ c. The results or the”
mines ere given in Table V. .

Willard end lab: (21) seemed the 1mm reoidne to be sirooninn
pyrophesphste . the: reported those residues to here I-Eey potterns ‘
identiosl ts resiaues obtained by the precipit’stion of sirooniun by
the use or orthophosphsts ion. the results of the sets phosphate
method gore s residue weight st 0.3139 pus, while the Whosphste
Isthod being investigated, gm e residue might at 0.3151: an.

Both these lethods [eve high results «synod to the sendelis soid
some, union weld yield s theoretio‘sl sireoniu pyrophosphste residue
of 0.3051 wees.

TABLE?

RESULTS 0' 211330110}! AMI-ISIS cam: IETA MGR ACID
AS PREDIIATIIG mom

_.... A

 

—.—-T

 

 

fl '—

, 11' A

 

 

 

’ ' > . Wt. in ‘
arm ot‘ in ‘ In. or :01 1mm om of
Sale 210. falcon Cone. Sole. [3,0, Residue ZrPIO,
1 04MB 3‘.‘ 25 0.3203 0.3050
2 (LIME 3.6 ’ ‘ 35 0.3128 0.3050
3 0.1.h18 3 .6 25 0.3103 0 .3050
A *‘4 A“ ohm-M18 .‘6 W k 4M0 22 _ 0%

 

 

 

Average 0.3139

7.; - _. ‘- A .. Ak _.__._ A

 

we-

 

13

The precipitate for-nod, when disodizm dim'drogon hypOphosphste
was aided without addition of acid to s solution or ziroonyl nitrate,
was investigated. Three 2h.9h m1 aliquots of the standard zirconium
solution (0.11418 grams of 21-0. per 21:59.; s]. or solution) sore diluted
to 155 ll Ind 55 ml of 0,05 s disodim mom-om Whosphoto sore
added to sub saple. This volume of disodim dihydrogen hypOphosphate
represents on some" of MOS seeming the preoipitste to be ZrCfianfl"
The suples were washed by doesntetios with smell portions or. water,
treated with filter pulp, filtered end ignited to content miazt at
Iowa 6. The results of those snelysoe ere gives in Teble '1. These
analyses indicate s sole ratio of phosphorus to sirooniu of less
then two. A 0.05 I! disodim dihydrogen maphosphste solution hes s
pH of ltd. The sole rstio of phosphorus to simniml of less then two
eighties due to Whale of the siroonius to the hydrous oxide or
oepreoipitstion of six-cowl nitrate. The possibility of hydrolysis
sss invostigsted, by diluting tee 2h.9h sl eliquots or the standard
siroonius solution (0.11le guns st 230.) to 150 :1 sad heating on s
ste- bsth tor .1 1/2 hours. The diluted elitoots "fined clear.
Therefore, it see sssused thet as hydrolysis took plsoe during the
precipitstion by dilution Wagon Whosphste.

Precipitstions of siroonius hypoPhesphete were node by soloing
21:31; :1 sliquots of the standsrd siroonims solution (0.1h18 greens
are.) to solutions or disodim dihydrogen hypophosphsto. The disodim
dirty-drug» hypophosphste solutions oontsined s 52% expose, sewing
the prooipitete to be 2mg” m or the median diludrogon

,TfiBL-EYI

GDJNWRIC, RESULTS 0313A” BI ADDDTG DISODIUH DMROGEH
WOSPEME 1'0 ZIRCWIL [PIRATE WITHOUT ADDITIOg W ACID

.4 _1 _._._ .A‘ ._._._ m *4. ——
‘ _.._. ,

4" ..___n... #4 .4‘ _ _..__.

_ , A w ‘r—

I 'n m

 

can o: no, tsken ' - _ 0.11m: om: 0mg

Orees or ignited residue ' 0.2865 0.2851 0.2886

momma. weight tor ‘ .

‘ (m): 1.0: (arm) - , 0.2235 0.2235 0.223;

Theoreticel vol t for . ' .
0.3051 0.3051 0.3051

‘ ZrPfi, (pus

~4—— ._k __ A4.

 

v ,7 W, VF , WW

hfiophosphste solutions we acidified with 100 ml of somentrsted
ivdroohlorie «14 m1 «mm to 17; n1; An eliquot of the standard
zircon-1m solution see edded to each of the eoidifled disodim di-
mer-om hypophoapmu solutions. The resulting moipitetes um
digested, treeted Uith filter pulp, filtered, mhed end ignited to
oonetent weight st 105066 . Tue edditionsl preoipitstione sore «retried
out is e siniler tanner, except that the disodim dihwarogen hypOphos-u
phate solutions were diluted to 175 I1 without edding said. These
staples, me then treated emtly the same as the ecidu'ied mp1“.
The results or these eulyees ere tabulsted in Tehle VII.

 

 

TABLE m

WWI? RESULTS MAINE) BI ADDEG ZIRCOIEI'L EITHER
T0 DISODIU! DIEDROW HIPOPEOSPKATE ‘

fl W. W Y w ——— ————
A A...__. .4_. A... ‘__._. ._. A.“ w

W .1, v , fi— —— — W . “"'

n. o: 0.05 n n.2,”).

SS'nl. lhflfi causes 55.0 55.0 55.0 55.0

111. 3,0 added _ _ 20 20 120 120
Volume at 2191 added _ 100 mo 0 0
Final Acidity man 5.?“ 5.95! - ..
701m of etendsrd Zr.

solution eddcd . 25.91: 2b..95' 22:32: 213.91;
Totsl volume ml. ' 200 2-30 2‘1!) 200
Residue weigzte in gene 0.31148 0.3137 0.3207 0.3211

has calculsted for 23.0, 0.3051 0.3351 0.3051 0.3031

g A A _~1._‘ ‘— L _.._._ . _ __ ‘u- A- A__A_ _.._ .1.._..__ __—_4_

WW ___ "1 W W

Detersiaetion er the Phosphorus to Zirconium Retio
‘ in the Precipitate

In en ettmpt to expldn the high grevinetrio results, s properation
9: smonyl dikvdr'ogen wphupmu eee no. end enslysed in the
following senner. Five hundred ll of. standard sireoniue solution was
trested with 600 ml of moantreted Mahler“ eeid end 100 ml of
0.05 I disodiuel dihydrogen hypophosphete. This volume of dieodiam
Wm mophoephete represents s 521 emcee, meaning the precipi-
tste to be m;&.. The sireonim hypophoephete use weehed by
decentetien emu two 300 .1 portions of he Wehlorio acid, tum-m
end sir dried for 30 days. The sir-t dried precipitate still gave of!

‘.

Neu-

.‘p

.r.v-

 

 

16

vapors of hydrogen chloride sitar 30 days sir drying.

' for the mslyeis of the eirconium mrpo'ohosphate , i‘mzr samples
were fused with sodiun pee-suds in 111:: kg]. cruo ihloe lined with head
soditm eerbonete (5 ) . The (used simples me leached with hot water
and the residues are slain fused end leachod with hot water. The
respeutivo leechinge (rm the-first and soooni fusions were embined
eni oonomtretod to s wlme or zoo ml. ' Asugm 3.1m preoipitnte '
sppeerod, which was removed by tiltrstion am disordod. m filtrates
were snalyzed for phosphorus by a double precipitation of “mania
main phosphete (ll). '

The residues were dissolved in 1:3. hydrochlorio acid and diluted
to 200 ml. These solutions, oomtsin'ms the ekeonim, were treated
with 15% nmdelio said and the precipitates of zirconium mandala-to
were filtered, ignited sari unified es zirconium oxide. Zirooniwe
smple umber three wes lost on concentration. the results are tabo-
lsted in Table VIII.

IABLEYIII

mmumm RATIO U AIR m0 imam 51810303733
‘ 590193033!er PPJEIPITAEED PROM ACID WTIOH -

 

Sample weights 0 50.96 0.5093 0.5101; 0.5101

areas of 11-0. 0.11:60 0.11468 «- 0.1063

Roles of 21‘ 0 .001185 0.00.1191 - 0.000863

arms et Ewe, 0.3028 0.27104 0.2832 0.3021

Holes 0! P _ 0.002721 0.002%? 0, 51:5 0.33271};
3.

Hole Pflr ‘ 2 .296 2 .070 "r"

1'?

In an sttenpt to obteli better {300013 .on for the phosphorus-
siz‘uoniun rétio, four staples of the air dried. zircoqyl dihyzirogan
hypophozphato were analyzed by the .folloflog prooedm'o. The samples
were fused vi h 7 grams of sodium ombnmto in plothuu o moibloe.

The fused masses were leached with hot vsunrto‘. . l‘ho reel: was we": flood
spin with ”dine cerhonete and. lowhed with hot water. the combiood
leaching: were enelyeed for phosphorus by s double precipitation of
”poems moniue phosphste end ignition to magnesium pmhoogghate
(11). The residues were digested in s fixture of nitric end sulfuric
said. The solutions we ooaqoentrsted end on neutralization with
sodium hydroxide, the mot-stool sireonium ondoo preoipitatei. The
precipitated zirconiun oxides ware renovofl by filtration and dissolved
in hydrochlorio said. Those solutions were i‘efifllf‘ifi‘zd for :irconime by
precipitetion as zirconimu mmrlolate (12.). Tho zirconium nmiolato
precipitates euro ignited end mzighyd as :iroonim ondde.1'ho romlis

are given in Table II.

TABLE II

PHOSPKDE'IE S-EIRCOXIZDE RWIOS (I? ZIRE‘ 02m mom HEMOSPKATE
PITIPLHL .23 1'31. 3‘! AC. ’2‘ SOIJJTIOK

“—- -—-‘—A A n#-..-.._._ ..__ ‘— _‘

 

~——_—‘
w -‘ ‘Q-a. en'WMI-C‘m-u‘ W ““‘“ _..___. _V.““‘_

 

I II III
arms Zrfififi. teken 0.5011 0.50015 0.5008
drone 213.1930, 0.3388 0.3566 0.3537
Holes of P '3 0.003221; 0.003201. 0.003177
am.- 2:03 0.18130 0.13m 0.1623
Holes o! 2r 0.031593 0 .oomoé 0 .001311

P/‘Zr retio 2 .159 2 .169 2 .3432

WA-
A.._._ A _.___...____ A A

--

 

18

The nurture "ports that ignition of medium dim-dragon
hypojphmphlto fluids o nixtnrc at Iodiml metaphoaphau, phoophina ,
Iodin- phosphido and hydrogen (19). I. 382421. (1.9097 gram) or pure
madm- mum-om myophoaphm mm.“ m ignited a looo°c
for two hours. The union. nighod 1.1792 can, while comm-ion
to lodiu uttphuphnto, would yidd 1.21.06 gnu.

In order to detailin- it phoaphoru in In“ on ignition, tun
lupin of air driod zirconium Wsphm precipitated from antral
solution mo ignited at 1.000% in I nun of mgon. tho "opt gun
at. pound throng: a 55 solution or ”dim hypochlwito. 2h. «4m
hypochlorito ablation m trotted with min-1o aid and dip-tad. the
«lotion m tasted for the penance of tho orthopholphnu ion by the
addition of n ”lotion of mania nomad. . lo gain results were
Ohm.

I-Ray Diffraction Studio: of Precipitatos

x-aq alumna puts-n- are no. or the ton-um (a) .1:-
dried Iirooniu magma-pm. ”mama from acid solution,
(b) unit“ Mania hpOphocphoto moipitatod from acid ”lotion,
(0) air driod zirconium hypophlphnto wooipitoud uthont addition -
of mid. (d) ignited Iirooniun hypophoaphm precipitated ultimo
addition of Mid, (o) ignited zirconium not: phosphato and (I) :iroonium
odds prepared from xirooniun nandohto ignition. The amplu were
prepared me diffraction by grinding in an agate mortar to approximately

19

100 meek. The samples were than packed in 0.3 mm diameter X-ray
capillaries. The prepared capillaries were centered in the circular
m M united for 8 hours of. 35 kt. and 3.6 ma. on 1 Earth
Mariam Phillip! inflame“. The davuloped pattern were read for
the 1060341011 0: the lame intense lines and the relative intensities
of the" lines mentioned. the pattern- of the ignited :iroonima‘ , I
bypaphOIphmI obtained tron acid solution, the ignited niroohim
mmephete obtained 'Iithout eddition of acid, end the ignited
zirconiu- orthe phosphate were idmticol. Io diffraction mm om
obteined for the air-dried eirooniun maphoephm precipitated from
acid solution Ind the m- driod eirconiun hypophoephete precipitated
without addition of mid. lo zirconim oxide line: were noted in the
potterne of the ignited lit-comm phonpheue. The result. of the

1-way tort are given in Table 1.

rm 1 ' ‘
x-au um names cr Imam) zmcoumi mosmnzs

H w ._.__‘ g...
Wm ~—

A— A; ___ h..—
.w w

zirconium we Wt- Bypephoephete Zirconiu- Eypopho lute

 

 

 

rho-pm , {Intro} Solution) , (mmI Solution
1.8% ' 1.838 1.833
2.127 2.118 1.110 f
2.1.00 2.378 2.380
1.630 2.618 2.620
3.055 3.000 3.035
3.595 3.578 3.580
L795 {.773 L780
h. S .898 11.903
5. 8 5.310 5.5318
5.800 5.765 5.775

 

 

. 4.
. q...
6 - -

 

 

H-

 

 

 

. *
v .

 

2O

‘ ammo-1. and p3 Titeatione

summer-10 titration: were made to determine the equivalence
point when a, award solution 0! dieodiun dihydro gen thosphate
1- umted not: attended aolution o: zit-cow]. nitrate. In ”dear.
to minimise the .fllution error, the concentrated nimonyl nitrate
aolution (0.2176 3) ya need. The procedm need is carrying out. the
omtmtrie titration. m to mm a m m of nolee of di-
”dim dihydrozen nympho-spin“, dilute to 160 :1 and then read the
refinance of the ”lotion after each named addition or them].
nitrate. 101 minute» we mounted on an Industrial Sinatra-ante
cmdmtivity Bridge model Baal! . The reciprocal of resistance
(conductance) was then plotted 13mm :1 or tier-at.

The titration of dieodim We“ hypophoephate with airway].
nitrate (graph 1) ghee on break: corresponding to ratio. at 5%.; ,
at 2.81 :1 and gig at 5.60 :1. The rupeeti'n theoretical valuea
- m 3.87 I1 Ind 5.": a1. mum:- eleotrodea were used in this titra-
tin.

Aqueoue oondmtmtrio titration: of the aireowl nitrate aolution
. ‘1”! the diaodim dihydrogon mphoephate eohtion gave inconelueive
mum. '

It val thought that by cuppa-ling the dislocation of the di-
hydrogan mhoqahato ion, a titration «me no: Iignifioanoe «on
be obtained. one hundrednletnethaul 0011198110! distilled“
were added to 2.0 III of 0.2176 n airoowl nitrate thus eating a

MHOS

x :04

‘CONDUCTANCE

0.94

0.86

0.78

0.70

0.54

0.46

 

 

  

 

 

r I ' F l I ‘ T 1 I I I I 1 I
— ——4
*— _—

_ _ L l l I 1 l 1 1 L
O I 2 3 4 5 6 7
MLS. OF 0.2176 M Z9RCONYL MTRATE ADDED
3mm z. CONDUCTOMETRW TITRATION OF 4.3.88

MLS. OF 0.05 M DISODIUM DIHYDROGEN vao-
PHOSPHATE WITH ZIRCONYL NITRATE

21

0.001145 ll liroonurl nitrate solution which m 33% in methanol. Thin
lethmol mum at smonyl mute was titrated with the 0.05 l
dilodinl dinydrogon mophoepheto solution. Platinum electrode: were
used in this titration. the break in the our" 1% 9.5 Ill tpp‘roxinnul
e ratio of $233. (graph 2). The theoretical value for the break in
8.? ml. the remit: of this titration indicate that the phosphorus to
Zirconium mole ratio in tho precipitatu in greater than two. firavinotrio
om (ram. v1) carried out in a nanner einilar to this oonduotonotrio
titration gun e phosphorus to zirconim mole ratio of less than too. '
The yovimetrio work was done in equeoun nodia while tho oon'inotometrio
titration was! carried out in I 331 methanol solution.

A pa titration was made to datomino it tho no." or the 3.9.0."
ion was the anionic apeoios in the precipitate. Thin p8 titration was
carried out by titrating 10 ml 01‘ a 0.0105 H eolution of liroozwl
nitrate Iith I 0.05 I disodiun dihydrogen Who-phat solution using
a room node). 0 pa neter (graph 3). I: the precipitate 1. (now.
or ”Pfi” hydrous: ion. would he released Ind a drop in pH Ihould be
detected before the equivalence point . This titration 1m increasing
)3! values If“: each addition of dioodium dihydrogon hypophoephate.
The elopo of this pl mu remain: essentially constant, thus support-
ma the ext-tense a: the no.0." ion a the admin spociel in the
precipitate.

MHOS

X l04

CON DUCTANCE

5.0

4.8

4.6

4.4

4.0

 

 

 

 

 

I j I I I I I I I T I l I
l I 1 I 1 l I l L l I I L
s 8 IO l2 l4 I6

ML5. 0.05 MDISODIUM DIHYDROGEN
HYPOPHOSPHATE ADDED

GRAPH 2. CONDUCTOMETRIC TITRATION OF
300 M‘LS. OF 0.00l45 M ZIRCONYL NITRATE IN

33% METHANOL WITH DISODIUM
DIHYDROGEN HYPOPHOSPHATE

2.80

2.60

2.40

2.20

2.00

l.80

I.60

L40

 

 

 

4 I I l I l J l T

 

 

2 4 6 8 I0 I2 I4 I6 I8

ML. 0F 0.05 M DISODIUM DIHYDROGEN
HYPOPHOSPHATE ADDED

GRAPH 3. pH TITRATION or: ID ML. OF

0.0345 M ZIRCONYL NITRATE WITH
DISODIUM DIHYDROGEN HYPOPHOSPHATE

‘3
4

DISCU‘T' 0”

t
F
is?

The exporimontal work indicates that precipitates of varying solo
ratios of phosphorus to zirconium are obtainod than dioodima dihydrOgon
hypoghoophata am zircomrl nitrate are allow-i to roast. The methods
investigated. in this work for the dotemination of zirconium is
empirical and depends on the aim of tho zirconiIm couple. The factors
which influence the composition of the precipitate are: acidity of
the aolution, art? of addition, occlusion and posoibly the coprooipi-
tation of hypophosphata . Ia solution more the concentration of hydroc
chloric acid is greater than 1.5%, the zirconium is mtitativoly
precipitated by the addition of a 5035 one" of diaotiium dillydrogon
mpophoaphato. Imition of this prooipitato to constant weight and
multiplication of the residue weight by tho empirical factor 0.3329,
will yield tho pm or airoonium in the sample. This empirical factor
on only to and When the amount of zirconium present ia near Mi 31111--
pane. Tho precipitation of. airconiua by diaodim dihydrogon m'popnoao
phato in aa complete as precipitation by the use of mandolio aoid.

Tho gravinetric reenlte from acid solution and the analyuie of
tho air-dried liroowl wwdrogon ‘twpophoaphato for phosphor” to
airooniuo mole ratio ehov a ratio water than two. thia ratio is
probably due to occluded and adsorbed diaoditm dihydmgcn hypophosphato.
Wham smaller emlea o! airoonim are precipitated, the phosphorus
to zirconiu I010 ratio val wallet, but reaainad greater than two.

In afloat, I titular ample aize new loea praoipitato, IOTO thorough
melting, and lease occlusion or adsorption of tho precipitant: reagent.

2.3

Tho precipitate (mad, when a diaodim dimdrogem hypop‘maphato
aolntion to added to a aolution of “room. nitrate withoot addition
or acid, has a phosphor” to aireonin aole ratio between one and too.
A pa flock of thin reaction aimad that the 3.11.0." ion a the anion
quotes to tho precipitate. a ponihle aaplanatiou or thia phon-
iphom to zirconium role ratio of Ion than too would be copraoipi-
tetion or airoonyl aitrate or airoowl chloride by tho sirooniun
dihodrom movbuphm-

Two equivalence point. oormpoomg to compound: zro(n.r.o.).
and magma.) are indicated by oonduotoaetrio titration: than
airconyl tone m edood to oitvdropn mophoaphato 1m . Grain-atria
"cults obtained by adding liroouyl ion to an emu a! median
“hydrogen hypophoqohate give a ouponnd uth a phuphom to zirconiu-
Iole ratio or greator than two. rho tiret break in the emotomtrio
m com-pending o zro(n.r.o.). could be an unstable Specie!
which upon addition of an emoaa of M“ ion in transformed to a more
atabla oupozmd, 21-0(H.P30.).

llmnthal (2) ha {mulatod role: for a notes: or zirconitm
chantry and points out that the Zr“ ion has bean reported to amt
only in atrong non-coupled.“ aoid «lotions. The present work in in
emmnt with Blunonthol'a (2) mton of airooniua chemistry, aims
in this Mitigation the precipitate tom! as: found to be 213031930...

SEfiW

2h

The composition of tho precipitate resulting Ira airing Midi-
ticd solutions of lirconwl nitrate and diaodiwa dihydrogan mophoe-
phate m dotcrained. The precipitate wee loom! to hm tho following
proportieea a varying cmpoeition, the 3.150." ion an the anionic
apooiea , a phoephome to circoniun aole ratio of approneetely two
and a coupoeition at. Qproxinatcly ZrGJfi” The imited aircomrl
dihydrOgon maphoapbate and ignited airconim ortho phoephate were
found to have idmticel I-rv diffraction pattern. the varying
composition of tho precipitate , tomed by adding dieodiul dihydrogon
moprIphate to eiroonyl icne , aakee thie precipitate unauiteble for
a quantitative detonation of airconim .

LITERATURE CITED

25

1. Alford W.C. Shapiro L. endWhite C. E. 111131.611”. 2
ling (19; J l O 3 .2!

2. Blunenthal, w. 3., Ind. Eng. Chem" go, 528 (19510.
3. own, 2., [101113531 State College ‘l'hosie (191:7).

it. Proacniue, V. and leader G. 'fimdbuoh Der Analyticchcn Chomio,‘
Vol. hb, Springer-Jorlog” Berlin (1950).

5. I‘m-nan, I. 1., 'Standtn'd nothode ci’ Chemical Anelycie,‘ fifth
Mtion, p. 1095, low I'm-k, D. Van Hoctrand 00., Inc. (1939).

6. mm, 1. 5. ml White, c. 2., Anal. Chem” 35, 1886 (1953).
7. m, R. 3.. Anal. shun... a. 1579 (1919).
8. Humor, 0. and ficrsfcldJ" Z. Lnorx. Chen" £13, 92 (1913).
9. norm, A. 11., Ana. cm... g5, 1331 (1953).
10. Klingcnborg, J. J. and Pepncci, a. 1., Anal. cm... 33, 1861 (1952).
ll. Iclthofl‘, I. I. and Bendoll, I. 3., "textbook of Quantitative
Inorganic Anelyaie ' p. 353. Third Edition, Hmillen co.,
1. 1.. l. 1. (1952).
12. Kunine, c. 1.. Anal. cm... 12, 376 (191a) .
13. Lomngar, a. and Choleki, 1., J. An. Chem. Soc” 11, 2385 (191.9).
1).. loallar, 2. and omen, o. 0., J. Al. on... Soc" 15, 3572 (1953).
15. Hoeller, r. and mm 0., Anal. cm... 33, 1351) (1952).
16. Oelper, a. 1. and ningonborg, J. J., Anal. cm... 2;. 1509 (191.9).
11. rum, 1. 11.. nomm cm. College Thanh (191.9) .

18. Papucci, R. O. noiahnen, D. 8. and ningenberg, J. J., Anal. Chem,
25. 1158 (1953).

19. can», 2., Ann. 131, 322 (1877).
20. Timur, n. J. and Yoizt, A. 3., J. An. cm. Soc” 11, 3197 (1951).
21. Willard, n. and Hahn, a. a., Ann. ohm... g1, :93 (19119).“

A\

 

 

A sum: 09 211902911211 319091113999...

31*

man 1'. Bolt

AH ABSTRACT

Submitted to the School of Graduate Studies of Michigan
State College of Agriculture and Applied Scianoa
in partial fulfillment of the requirements
for the: demo of

MASTER W 33 1‘2“" LIE
Depu'b‘nent 01’ Chemistry

fear 1951;

Approved

Ramon I. Roll:

 

A study m and» to determine the qualitative and wantitati‘m
properties of the precipitate formed when siroomrl nitrate is treat-ed
with a solution of dilodinn dihydrogen hypophosphnte . T‘m precipitate
was found to have the following chanteristiou a varying composition
dependent on the mount of Iiroonim preoipitated and the order or
addition, quantitative insolnbility in (15-10) I hydrochloric acid and
an @prox'mate phosphorus to zirconium ratio of two.

I-qu diffraction patterns show the ignited precipitate to be
identical to ignited zirconium ortho phosphate. The airodriod zuoomvl
dihydrOgen hypoPhoophate was found to be morphono to I-rays .

Conductometrio tetrationl give 1 break corresponding to a phos-
phorus to sireonim ratio of approximately two. A pH titration shown
the precipitate to have the 33,330." ion as the anionic species.

The composition of the precipitaio mm found to be appromately

Zr033P30..