Sie sind auf Seite 1von 9

STP148E-EB/Jan.

1960

Tentative Methods of Test for


PHOSPHATE I N INDUSTRIA L WATER1

ASTM Designation: D 515 - 60 T


ISSUED, 1955 ; REVISED , 1958, I960. 2
These Tentativ e Method s hav e bee n approve d b y th e sponsorin g com -
mittee an d accepte d b y th e Societ y i n accordanc e wit h establishe d proce -
dures, fo r us e pendin g adoptio n a s standard . Suggestion s fo r revision s
should b e addresse d t o th e Societ y a t 191 6 Rac e St. , Philadelphi a 3 , Pa .

Scope (6) Al l o f th e method s ar e base d o n


2 reactions tha t ar e specifi c fo r th e
1. (a ) Thes e methods " cove r th e de - or/Aophosphate ion . Preliminar y treat -
termination o f dissolve d phosphate s i n ment is included for removal o f color and
industrial water . Th e followin g fou r turbidity, an d heatin g i n th e presenc e
methods are included : of stron g acid s i n th e gravimetri c an d
Sections volumetric method s i s include d t o con -
Referee Method (Gravimetri c Method ) 5 to 11 vert mos t polyphosphate s t o th e ortho
Non-Referee Metho d A (Volumetri c
Method) 1 2 to 18 form. A s described, th e gravimetri c an d
Non-Referee Metho d B (Colorimetri c volumetric method s determin e al l dis -
Method) 1 9 to 27
Non-Referee Metho d C (Colorimetri c solved phosphate s that ca n be dissolve d
Method) 2 8 to 36 and converte d t o th e ortho for m b y th e
prescribed treatment . Non-Refere e
1
Under the standardization procedure of the Method B cover s th e determinatio n o f
Society, thes e method s ar e unde r th e jurisdic - only 0r/Aophosphate , wherea s Non-Ref -
tion o f th e AST M Committe e D-1 9 o n Indus - eree Method C covers the determinatio n
trial Water .
2
Latest revisio n accepte d b y th e Societ y a t of bot h ortho and tota l phosphate. Selec -
the Annua l Meeting, June, 1960 . tion o f th e metho d t o us e fo r a specifi c
Prior t o thei r presen t publicatio n a s tenta - water depends on its expected phosphat e
tive, thes e method s wer e publishe d a s tenta -
tive fro m 193 8 t o 1943 , bein g revise d i n 194 0 content.
and 1943 . The y wer e publishe d a s standar d
from 194 3 t o 1955 , bein g reverte d t o tentativ e Definitions
and20revise d in 1955 .
Non-Referee Method A is essentially iden - 2. Fo r definition s o f term s use d in
tical i n substanc e wit h Metho d A , an d Non - these methods , refe r t o th e Definition s
Referee Metho d C i s simila r i n principl e bu t of Term s Relatin g t o Industria l Wate r
differs i n detai l wit h Metho d C , publishe d
jointly b y APHA , AWWA , an d FSIW A i n and Industria l Wast e Wate r (AST M
"Standard Method s fo r th e Examinatio n o f Designation: D 1129). 3
Water, Sewage , an d Industria l Wastes , Tent h
3
Edition, pp . 166-16 7 an d 169-17 0 respectively , Appears h i thi s publication , se e Content s
Am. Publi c Healt h Assn. , Inc. , Ne w York , in Numeri c Sequence of ASTM Designations a t
N. Y. (1955) . front o f book.
Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018
Downloaded/printed by 237
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized. 17-01
Copyright© 1960 by ASTM International www.astm.org
238 TESTS FO R PHOSPHATE I N INDUSTRIA L WATE R ( D 515 )

Purity o f Reagent s The latte r i s ignite d t o magnesiu m


3. (a ) Reagen t grad e chemical s shal l pyrophosphate and weighed.
be use d i n al l tests . Unles s otherwis e Interferences
indicated, i t i s intende d tha t al l re -
agents shall conform t o the specifications 7. Phosphit e interfere s by conversio n
of th e Committe e o n Analytica l Re - to 0r//z0phosphate . Arseni c an d vana -
agents o f th e America n Chemica l dium compound s ar e precipitate d alon g
Society, wher e suc h specification s ar e with phosphate , an d mus t b e removed .
available.4 Othe r grade s ma y b e used , Precipitation o f th e ammoniu m phos -
provided i t i s first ascertaine d tha t th e phomolybdate i s retarde d b y hydro -
reagent i s o f sufficientl y hig h purity t o chloric, sulfuric , o r hydrofluori c acid s
permit it s us e withou t lessenin g th e and thei r ammoniu m salts , s o then: use
accuracy o f the determination . in samples prio r t o th e determinatio n o f
(&) Unles s otherwis e indicated , refer - phosphate should be kept to a minimum.
ences t o wate r shal l b e understoo d t o Reagents
mean reagen t wate r conformin g t o th e 8. (a ) Ammonium Hydroxide (s p g r
Specifications for Reagent Water (ASTM 0,90}.—Concentrated ammoniu m hy -
Designation: D 1193). 3 droxide (NH 4OH).
Sampling (0) Ammonium Hydroxide (1:1).—
4. Collec t th e sampl e i n accordanc e Mix 1 volume of NH 4OH (s p g r 0.90 )
with th e applicabl e metho d o f th e with 1 volume of water.
American Societ y fo r Testing Materials, (c) Ammonium Hydroxide (1:19}. —
as follows: Mix 1 volume of NH 4OH (s p g r 0.90 )
with 1 9 volumes of water.
D 510—Sampling Industrial Water,3 (d} Ammonium Molybdate Solution. —
3
D 860—Sampling Wate r fro m Boilers,
D 1066—Sampling Steam.* Dissolve 11 8 g o f molybdi c aci d (8 5
per cen t Mo0 3) i n a mixtur e o f 400 nil
REFEREE METHO D of wate r an d 8 0 m l o f NEUO H (s p g r
(Gravimetric Method ) 0.90). Filte r of f an y insolubl e matter .
Prepare a secon d solutio n containin g
Application
400 ml of nitri c aci d (HNO 3, sp gr 1.42)
5. Thi s metho d i s applicabl e t o al l and 60 0 m l o f water . Whil e vigorousl y
industrial water , but i s best suite d whe n stirring th e HNO s solution , slowl y ad d
the sampl e take n fo r testin g contain s the molybdate solution. Let th e mixture
10 mg or more of PCX . stand fo r 24 to 48 hr; then filter through
Principle o f Method a sintered-glas s funnel .
(e) Ammonium Nitrate Solution (20 g
6. Tw o successiv e separation s o f
per liter).—Dissolv e 2 g o f ammoniu m
0r//wphosphate io n ar e made , firs t a s
nitrate (NH 4NO3) i n wate r an d dilut e
ammonium phosphomolybdate an d the n
to 10 0 ml.
as magnesiu m ammoniu m phosphate . (/) Hydrochloric Acid (s p g r 1.19}. —
4
"Reagent Chemicals , America n Chemica l Concentrated hydrochlori c aci d (HC1) .
Society Specifications," Am . Chem. Soc., Wash-
ington, D . C . For suggestion s o n the testin g of (g) Magnesia Mixture. —Dissolve 5 0
reagents no t liste d b y th e America n Chemica l g o f magnesiu m chlorid e (MgCl2-6H 20)
Society, se e "Reagen t Chemical s an d Stand - and 10 0 g of ammonium chloride (NH4C1)
ards," by Josep h Rosin , D . Va n Nostrand Co. ,
Inc., Ne w York, N. Y., and the "Unite d State s in 500 ml o f water. Ad d NH 4OH (sp g r
Pharmacopeia.'' 0.90) i n slight excess, using litmus paper
17-61

Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.
TESTS FO R PHOSPHATE I N INDUSTRIA L WATE R ( D 515 ) 239

as indicator , an d allo w th e solutio n t o solved phosphat e i s desired . I n thi s cas e tak e


stand overnight . I f a precipitat e de - a representative , well-mixe d sample .
NOTE 3.— A clea r aliquo t ca n normall y b e
velops, filte r befor e dilutin g t o 100 0 m l expected afte r coagulation . However , in som e
with water. samples, tha t is , tannin - o r lignin-treate d
(ti) Methyl Orange Indicator (0.5 g boiler water , removal i s no t complete . In suc h
per liter). —Dissolve 0.0 5 g o f methy l cases ad d 2 t o 4 m l o f sodiu m hypochlorit e
solution ( 5 pe r cen t availabl e chlorine , phos-
orange in water and dilut e to 100 ml. phate-free) an d boil the sample for an additional
(*) Nitric Acid (s p g r 1.42). —Con- minute.
centrated nitri c aci d (HNOs) .
(f) Potassium Nitrate (KNOs) . (b) Conversion of Poly phosphates to
(k) Silver Nitrate Solution (10 0 g pe r Orthophosphate.—To th e filtrat e an d
liter).—Dissolve 1 0 g o f silve r nitrat e washings ad d 3 o r 4 drop s o f methy l
(AgNOs) i n wate r an d dilut e t o 10 0 ml. orange indicator . Ad d 1 5 m l o f HNO s
(/) Wetting Agent. —Add 1 m l o f a in exces s o f that require d t o neutraliz e
100 per cen t activ e nonioni c liquid wet - the sample . Cove r th e beake r an d boi l
ting agent 5 t o 1 liter o f water an d mix . the acidifie d solutio n fo r a t leas t 3 0
min (Not e 4) . Th e volum e after boilin g
Procedure should b e betwee n 2 5 an d 5 0 ml . Coo l
9. (a ) Preparation o f Sample. —Meas- and dilute t o approximately 10 0 ml with
ure int o a beake r a quantit y o f sampl e water. Neutraliz e th e sampl e wit h
containing dissolve d phosphate s equiva - NH4OH (s p g r 0.90 ) an d ad d 5 m l of
lent t o no t les s tha n 1 0 nor mor e tha n HNO3.
50 mg of PC>4 . Concentrat e o r dilute
NOTE 4.—I f th e sampl e is known t o contain
with water , i f necessary , t o approxi - only or/Aophosphates , th e solutio n need no t b e
mately 10 0 ml (Notes 1 and 2). Add 4 g boiled. O n th e othe r hand , certai n comple x
of KNO 3 an d boi l fo r 1 min. Allo w t o phosphates ma y require a 6 to 1 2 hr digestion
stand fo r severa l minute s t o settl e th e period fo r complet e conversion.
coagulated materia l (Not e 3) . Filte r (c) Precipitation as Ammonium Phos-
through fine-texture, ashless filter paper 6 phomolybdate.—Heat th e solutio n t o
into a 400-m l beaker . Was h th e residu e 80 t o 8 5 C an d ad d slowl y 1 5 m l o f
twice with a minimum volume of water, ammonium molybdate solution , swirlin g
allowing th e funne l t o drai n completel y the beake r whil e addin g th e reagent .
between washings . Continue th e agitatio n unti l th e pre -
NOTE 1.—I f boilin g i s require d t o concen - cipitate starts to form. Allo w th e beaker
trate th e sample , the p H o f the resultin g solu- to stand quietl y for 1 hr at a temperatur e
tion shoul d b e adjuste d t o approximatel y the of 4 0 to 6 0 C, agitate again b y swirling ,
same valu e a s tha t o f th e origina l sample ; then se t asid e a t roo m temperatur e fo r
otherwise som e dissolve d phosphat e ma y pre - not les s tha n 1 2 hr . Ad d on e dro p o f
cipitate or precipitated phosphate may dissolve.
Use a 1 0 per cen t by weigh t solution of NaOH wetting agen t t o th e sampl e an d sepa -
or HNO » for th e adjustment. rate the precipitate b y filtration through
NOTE 2.—Omi t th e followin g coagulatio n a sintere d glas s crucibl e (wit h suction )
step i f a measur e of both precipitated an d dis - or throug h a medium-texture , ashles s
filter paper 7 (Not e 5) , an d was h th e
s
Triton X-100 from Rohm & Haas Co., and filter fiv e time s wit h NH 4NOs solution .
Pluronic L-6 2 fro m Wyandott e Chemical s Discard th e filtrate and washings.
Corp. have bee n foun d satisfactor y fo r this pur-
pose.
6 7
Whatman No . 4 2 filter pape r o r equivalent Whatman No . 4 0 filter paper o r equivalen t
has bee n foun d satisfactor y fo r thi s purpose . has bee n foun d satisfactor y fo r thi s purpose .

Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018 J7-81
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.
240 TESTS FO R PHOSPHATE IN INDUSTRIA L WATER ( D 515)

NOTE 5.— A strea m o f NH4NO i solutio n


from a was h bottl e shoul d b e use d fo r trans - Phosphate, ppm =
ferring th e precipitat e fro m th e beaker to th e
filter. Complet e transfer i s readil y effecte d i n where:
this manner. The use of stirring rods and police-
men shoul d b e avoided , sinc e the y caus e th e
precipitate t o smea r an d mak e it s remova l W = grain s o f precipitate, an d
difficult. S = milliliter s of sample used.

(d) Precipitation as Magnesium Am- Precision and Accuracy


monium Phosphate. —Dissolve th e am - 11. Balanc e reproducibility i n weigh -
monium phosphomolybdate on the filte r ing i s th e principa l facto r fro m th e
with a fin e strea m o f war m NH 4OH standpoint o f precision. Precisio n varie s
(1:1), collecting the solution in a 400-ml from abou t 3 pe r cen t fo r th e 10-m g
beaker. Adjus t th e volum e of th e solu - range o f phosphate t o abou t 1 per cen t
tion t o 10 0 to 15 0 ml, ad d thre e o r fou r for th e 50-m g rang e o f phosphate . Ac -
drops o f methy l orang e indicator , the n curacy shoul d equa l precisio n i f th e
add HC 1 to neutraliz e th e NH 4OH. A procedure an d application of the method
yellow precipitat e form s durin g acidifi - are followe d carefully .
cation bu t redissolve s whe n sufficien t
acid ha s bee n added . Continu e addin g NON-REFEREE METHO D A
acid dropwise beyond the methyl orange (Volumetric Method)
end poin t unti l th e precipitat e disap -
pears. T o th e acidifie d solutio n ad d Application
dropwise, wit h constan t stirring , 1 5 ml 12. Thi s metho d i s applicabl e t o al l
of magnesi a mixture . Continu e t o sti r industrial water , but i s best suited when
and neutraliz e th e acidit y b y ver y slo w the sampl e take n fo r testin g contain s
addition o f NH 4OH (1:1) . Ad d 1 0 m l 5 mg or more of PO4 . It i s more rapid
excess NH 4OH (1:1) fo r eac h 10 0 ml of but les s accurat e an d precis e tha n th e
solution. Agitat e wel l an d se t asid e fo r Referee Method , an d i t i s mor e time -
not less than 4 hr. Collect the precipitat e consuming tha n Non-Refere e Method s
on fine-texture , ashles s filte r paper 5 and B and C.
wash i t wit h NH 4OH (1:19 ) unti l fre e
of chlorides , a s indicate d b y lac k o f Principle of Method
turbidity o n addition o f AgNO 5 solution 13. Or/Aophosphat e react s wit h am -
to th e last portio n of washings. Transfer monium molybdat e i n a solutio n
the pape r an d content s t o a weighe d containing citri c acid , nitri c acid , an d
platinum or porcelain crucible. ammonium nitrat e t o for m insolubl e
(e) Ignition. —Char th e pape r a t lo w ammonium phosphomolybdate . Th e
temperature, bur n of f the carbo n a t a precipitate i s washe d fre e o f aci d an d
temperature belo w 90 0 C , an d the n then treated with sodium hydroxide. Ex-
ignite t o constan t weigh t a t 105 0 t o cess sodiu m hydroxid e i s titrate d wit h
1100 C . Coo l in a desiccato r an d weig h acid t o a n en d poin t havin g a shar p
the precipitate, a s Mg 2P2O7. color chang e at p H 7.5.
Calculation Interferences
10. Calculat e th e P0 4 equivalen t 14. (a ) Phosphit e interfere s b y con-
of th e dissolve d phosphate s i n th e version t o or^ophosphate . Arseni c and
sample, i n parts per million , as follows : vanadium compound s ar e precipitate d
17-46

Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.
TESTS FO R PHOSPHAT E I N INDUSTRIA L WATE R ( D 515 ) 241

along wit h phosphate , an d mus t b e (0 Nitric Acid, Standard (0.25 N) .


removed. Precipitatio n o f th e amoniu m Add 27. 5 m l o f HN0 3 (s p g r 1.42 )
phosphomolybdate i s retarded b y hydro - to about 70 0 ml of water and dilute t o 1
chloric, sulfuric , o r hydrofluori c acid s liter. Standardiz e th e HNO s agains t
and thei r ammoniu m salts , s o their us e the 0.2 5 N NaO H (Paragrap h (*)) ,
in sample s prior t o th e determinatio n of using th e mixe d indicato r (Paragrap h
phosphate should be kept to a minimum. to).
(6) Extremel y hig h concentration s of (g) Potassium Nitrate (KNOs) .
soluble iron , no t usuall y foun d i n in - (ti) Potassium Nitrate Solution (10 g
dustrial waters , dela y formatio n o f th e per liter). —Dissolve 1 g o f KNO s h i
ammonium phosphomolybdate . Thi s in- water an d dilut e t o 10 0 ml.
terference ca n b e minimize d b y usin g a (i) Sodium Hydroxide, Standard Solu-
citromolybdate solutio n twic e th e tion (0.25 N).—Prepare a 0.25 N solutio n
strength give n in Sectio n 15. of sodium hydroxide (NaOH) by diluting
a clarified , saturate d NaO H solutio n
Reagents with water , an d standardize . Stor e th e
solution i n a heavily-waxe d glas s bottl e
15. (a ) Citromolybdate Solution. —Dis- fitted wit h a two-hol e stoppe r carryin g
solve, withou t heating , 4 3 g o f am - a glas s sipho n tub e wit h stopcock , an d
monium nitrat e (NEUNOs) , 4 2 g o f a soda-asbesto s o r soda-lim e tube. 8
citric aci d monohydrate , an d 5 4 g o f (j) Wetting Agent—Add 1 ml of a 100
ammonium molybdat e ((NH^eMorO w • per cen t activ e nonioni c liqui d wettin g
4H2O) in 1000 ml of water. Add this solu- agent6 t o 1 liter o f water an d mix .
tion t o a mixtur e o f 20 0 m l o f concen -
trated nitri c aci d (HNOs , s p g r 1.42 ) Procedure
and 23 0 m l o f water . Ad d filte r pape r 16. (a ) Preparation o f Sample. —Pro-
pulp or a few drops of ammonium mono- ceed a s describe d h i Sectio n 9(a) ; how-
hydrogen or/&0phosphat e ((NH 4)2HPO4) ever, i n thi s cas e th e volum e o f sampl e
solution, boil for about 5 to 1 0 mm, then taken fo r testin g shoul d contai n n o les s
allow t o stan d overnight . Sipho n off th e than 5 m g no r mor e tha n 5 0 m g o f
clear solution. PO—.
(b) Methyl Orange Indicator (0.5 g per (£) Conversion o f Poly phosphates t o
Uter)—See Section S(h). Orthophosphate.—To th e filtrat e an d
(c) Mixed Indicator. —Grind togethe r washings ad d 3 o r 4 drop s o f methy l
exactly 0.25 0 g o f bromthymol blue and orange indicator (Not e 6). Add 1 0 ml of
0.156 g of phenol red h i a smal l mortar . HNO3 (s p g r 1.42 ) h i exces s o f that re -
Dissolve the mixed indicators b y addin g quired t o neutralize th e sample . Evapo -
a sligh t exces s o f 0.2 5 N NaO H rate th e solutio n t o drynes s on a stea m
solution. Ad d abou t 70 0 m l o f wate r bath. D o no t bak e th e residue , an d
and adjus t t o pH 7. 5 with HNO 3 (sp gr avoid spattering . Dissolv e th e residu e
1.42), preferabl y usin g a p H mete r t o with 5 0 m l o f wate r containin g 1 t o 2
determine th e en d point . Dilut e th e ml o f HN0 3 (s p g r 1.42) . Hea t t o dis -
adjusted solutio n t o 1 liter wit h water . solve th e residu e an d remov e an y silic a
(d) Nitric Acid (s p g r /.^.—Con - by filtration . Was h th e insoluble residu e
centrated nitri c aci d (HNOs) . with HNO 3 (1:99) , keepin g th e volume
(e) Nitric Acid (1:49}. —Mix 1 volume of washing s t o les s than 5 0 ml.
of HNO 3 (s p g r 1.42 ) with 4 9 volume s 8
Ascarite an d Caroxit e hav e bee n foun d
of water . satisfactory fo r thi s purpose .
17-46
Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.
242 TESTS FO R PHOSPHATE I N INDUSTRIA L WATE R ( D 515 )

NOTE 6.—Th e ste p describe d i n Paragrap h B = milliliter s o f standar d HNO »


(ft) ca n b e omitte d i f th e sampl e i s know n t o
contain n o polyphosphate s an d i f th e silic a
solution added ,
(SiO2) conten t i s les s tha n hal f th e PO 4 NI = normalit y o f standar d NaO H
content. solution,
N2 = normalit y of standard HNO 3 solu-
(c) Precipitation and Titration, —Heat tion, and
the solutio n t o boilin g and , whil e S = milliliter s of sample.
stirring, ad d 15 0 m l o f citromolybdat e
solution. Agai n hea t th e solutio n t o Precision and Accuracy
boiling and allo w it t o simmer for 2 to 3 18. The precisio n and accurac y of this
min, stirring th e solution intermittently . method var y appreciabl y wit h th e car e
Add 1 drop o f wetting agen t an d allow used i n washin g th e precipitate , th e
the precipitat e t o settle . Decan t th e standardizing o f th e standar d solutions ,
solution throug h a medium-texture, ash- etc. Wit h prope r attentio n t o details ,
less filte r paper, 6 retainin g th e bul k of precision shoul d be approximately 2 per
precipitate i n th e origina l beaker . Wash cent an d accurac y shoul d b e ± 1 pe r
the precipitat e i n th e beake r fou r o r cent o f th e phosphat e presen t h i th e
five times with 20 - t o 25-m l portion s of range indicated i n Sectio n 12.
KNO5 solutio n containin g 1 dro p o f NON-REFEREE METHO D B
wetting agen t pe r liter . Transfe r th e
precipitate t o th e filte r pape r an d wash (Colorimetric Method)
ten tunes with the KNOs solution. Plac e Application
the filte r pape r i n th e origina l beaker , 19. Thi s metho d i s applicabl e t o th e
add 5 0 m l o f water , an d dissolv e th e routine determinatio n o f 0r//t0phosphat e
precipitate b y slowl y addin g standar d in industria l water . I t i s best suite d t o
NaOH solutio n fro m a buret. Add about boiler feedwate r an d boile r wate r con -
5 ml excess. Add 1 ml of mixed indicator, taining 2 t o 2 5 pp m PO4 . Th e rang e
and titrat e wit h standar d HNO a solu - can b e extende d upwar d b y dilutin g
tion unti l th e colo r changes from purpl e the sample.
to yellow. Remove th e filter pape r fro m
the beake r an d rins e i t wit h water . Summary o f Method
Adjust th e volume of the solutio n i n th e 20. Thi s method is based on the photo-
beaker t o abou t 20 0 ml. I n direc t sun - metric measuremen t of th e yello w colo r
light o r h i fron t o f a n illuminato r of phosphovanadomolybdi c aci d de -
equipped wit h a fluorescen t dayligh t veloped i n th e sample . Thi s colo r in -
lamp, back-titrat e th e solutio n wit h tensity i s proportiona l t o th e ortho -
standard NaO H solutio n t o a light , phosphate concentratio n o f th e sample .
permanent, purple color. Interferences
Calculation 21. Thi s procedur e i s not suitabl e fo r
highly colore d water , suc h a s tannin -
17. Calculat e th e PC> 4 equivalen t treated boile r water , unles s th e colo r
of th e dissolve d phosphate s i n th e is firs t remove d (Not e 3) . Hig h con -
sample, in parts pe r million, as follows : centrations o f ferri c ion s interfer e wit h
this test , bu t generall y are no t presen t
Phosphate, ppm =
in th e wate r fo r which - this metho d i s
intended.
where:
A = tota l milliliters of standard NaO H Apparatus
solution added , 22. Photometer. —A spectrophotome -
Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018 17-46
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.
TESTS FO R PHOSPHATE I N INDUSTRIA L WATE R ( D 515 ) 243

ter o r filte r photomete r fo r us e a t 40 0 (filter wit h suctio n i f suspende d matte r


to 420 m/i. The range of the test depends is present ) int o a n Erlenmeye r flask . I f
on th e ligh t pat h lengt h o f the solutio n the sampl e contain s mor e tha n 2 5 ppm
being measured . Th e rang e specifie d i n P0 4 , us e a correspondingl y smalle r
Section 1 9 i s applicabl e t o tes t solu - sample. Add 25 ml of ammonium vanado-
tions measured h i a 20-m m cell. molybdate solutio n t o th e sampl e an d
mix well . Allow 2 min. for color develop-
Reagents ment. Measur e th e colo r absorbanc e
23. (a ) Ammonium Vanadomolybdate at 40 0 to 42 0 m/i wit h th e filte r photo -
Solution. —Dissolve 4 0 g o f ammoniu m meter o r a t 40 0 m/ i wit h th e spectro -
molybdate ((NH 4)6Mo7024-4H2O) i n photometer, using water as the referenc e
400 m l o f water . Dissolv e 1. 0 g o f am - sample. Recor d th e phosphat e con -
monium metavanadat e (NH 4VOs) i n centration indicate d b y th e calibratio n
300 m l o f wate r an d ad d 20 0 m l o f curve prepare d i n accordanc e wit h
concentrated nitri c aci d (HNOs , s p g r Section 24(c).
1.42). Add the first solution to the second
solution, mix , and dilut e t o 1 liter wit h Calculation
water. 26. Calculat e th e concentratio n o f
(b) Phosphate, Standard Solution (1 phosphate, i n part s pe r million , a s
ml = 0. 1 mg P0 4).—Dissolve 0.143 3 g follows:
of oven-drie d potassiu m dihydroge n
phosphate (KH 2PO4) in water and dilute Phosphate, ppm =
to 1 liter i n a volumetric flask.
Calibration an d Standardizatio n where:
24. (a ) Prepar e a serie s o f standar d C = parts pe r millio n phosphat e io n
phosphate solution s t o cove r th e rang e indicated b y th e calibratio n curv e
from 0 to 25 ppm. Prepare th e standard s for th e determine d colo r absorb -
by diluting suitable volumes of phosphate ance, and
solution (1 ml = 0. 1 mg P04) t o 5 0 ml S = milliliter s o f sample .
with water . On e millilite r o f phosphat e Precision an d Accurac y
solution ( 1 ml = 0. 1 mg PO4) dilute d t o
27. Th e precisio n o f thi s metho d i s
50 m l wit h wate r produce s a standar d
equal t o a 2 per cen t differenc e betwee n
containing 2. 0 ppm o f phosphate .
duplicate determinations , an d th e ac -
(b) Develo p colo r i n th e serie s o f
curacy i s equa l t o th e precisio n i n th e
standards a s prescribed h i Sectio n 25.
absence o f interferences.
(G) Measur e th e absorbanc e a t 40 0 t o
420 m/ i wit h a filte r photomete r o r a t NON-REFEREE METHO D C
400 m) M wit h a spectrophotometer , using (Colorimetric Method)
water a s th e referenc e sample . Plo t th e
absorbance value s obtained a s ordinates Application
and th e correspondin g phosphat e con - 28. Thi s metho d is intended primarily
centrations a s abscissas (Not e 7) . as a control test for waters containing 0.1
NOTE 7.— A separat e calibratio n curv e mus t to 1. 5 ppm PO 4. The range, which can be
be made for each photometer. Eac h curve mus t extended upward by diluting the sample,
be checke d periodicall y t o insur e reproduci - is fo r photometri c measurement s i n a
bility.
20-mm cell. The range can also be varied
Procedure by measurin g th e colo r i n cell s havin g
25. Transfe r 5 0 m l o f a clea r sampl e optical depths greater or less than 20 mm.
17-46
Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.
244 TESTS FO R PHOSPHATE I N INDUSTRIA L WATE R ( D 515 )

The metho d covers the determinatio n of Reagents


either orthophosphat e alon e o r tota l 32. (a ) Ammonium Molybdate Solution
phosphate (or^ophosphat e plu s poly - (25 g pe r liter). —Dissolve 2 5 g o f
phosphate). ammonium molybdat e ((NHOeMorC^ '
Summary of Method 4H20) i n abou t 80 0 ml o f water. Dilut e
the solution t o 1 liter with water.
29. (a ) O^0phosphat e react s wit h (V) Phosphate, Standard Solution (1
ammonium molybdat e i n a n aci d ml = 0.01 mg P0 4).—Dilute 10 0 ml of
medium t o for m a phosphomolybdat e the phosphat e solutio n ( 1 ml = 0. 1 mg
which in turn is reduced to a molybdenum P04) prepared in accordance with Section
blue complex with stannous chloride. The 230) t o 1 liter with water.
color i s proportional i n intensit y t o th e (c) Stannous Chloride Solution (25 g
phosphate concentration . per liter). —Dissolve 2. 5 g o f a fres h
(0) Onl y or/Aophosphat e form s a blu e supply o f stannou s chlorid e (SnCU -
color in the test. Such polyphosphates as 2H2O) i n 1 0 ml o f concentrate d hydro -
Pyro-, meta-, and tripolyphosphate , how- chloric acid (HC1 , sp gr 1.19). Dilute th e
ever, ca n be made to reac t i n the tes t if solution t o 10 0 ml wit h water . Filte r if
they ar e hydrolyzed to the ortho form b y turbid. Plac e th e solution in an aspirato r
boiling th e acidifie d sample . Thus , th e bottle havin g a glas s stopcock . Ad d a
polyphosphate content of a water can be layer of pure mineral oil 5 mm thick over
calculated b y subtractin g the orthophos- the surfac e o f th e solutio n t o minimiz e
phate foun d i n the unboiled sample from oxidation. Alway s drai n a littl e o f th e
the total phosphate found in the acidified, solution ou t o f th e stopcoc k befor e use .
boiled sample . Organi c phosphates hav - The reagent can also be preserved several
ing P—O— P bond s ar e als o hydrolyze d weeks b y addin g moss y ti n an d storin g
to orf&ophosphat e an d ar e measure d i n in a refrigerator.
the total phosphate determination . (d) Sulfuric Acid Solution. —Add 31 0
Interferences ml o f concentrated sulfuri c aci d (H 2SO4,
sp g r 1.84 ) slowl y t o abou t 60 0 m l o f
30. U p to 0.5 ppm iron, 25 ppm silica, water. Cool , and dilute th e solution to 1
and 100 0 ppm chlorid e will not interfere liter with water.
with th e test . Oxidizin g agents suc h a s
chromate, peroxide , nitrate , an d nitrit e Calibration
will bleac h th e blu e color . Interferenc e 33. (a ) Prepar e a serie s o f standar d
from nitrit e ca n be overcome by addin g phosphate solution s t o cove r th e rang e
0.1 g of sulfamic acid to the sample before from 0 to 1. 5 ppm. Make u p th e stand -
adding th e molybdate . ards by diluting suitable volumes of phos-
phate solutio n ( 1 ml = 0.0 1 mg PO4) t o
Apparatus 100 ml with water. One milliliter of phos-
31. Us e one of the followin g means for phate solution diluted to 100 ml produces
color evaluation: a standard containin g 0.1 ppm PO 4.
(a) Nessler Tubes, Matched, 50-m l (&) Develo p colo r i n th e serie s o f
capacity. standards a s directe d i n Sectio n 34(&) .
(o) Color Comparator, Commercial, with Measure the colo r absorbanc e at 65 0 m/x
permanent standards . of eac h standard wit h a photometer an d
(c) Photometer. —A spectrophotomete r plot th e absorbanc e value s a s ordinate s
or filter photometer suitable for measure- and the corresponding phosphate concen-
ments at 65 0 imt. trations a s abscissas (Not e 7) .
15-21
Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.
TESTS FO R PHOSPHATE I N INDUSTRIA L WATE R ( D 515 ) 245

Procedure (d) T o determin e total phosphate ,


34. (a ) T o determin e orthophosphate, pour 10 0 ml of the clea r sample in Para-
pour 10 0 ml of the clea r sample contain- graph (a ) into a flask. Add 4 ml of H2SO4
ing 1. 5 pp m PC X o r les s int o a 250-m l solution t o th e sampl e an d boi l fo r a t
Erlenmeyer flask . Fo r highe r concentra - least 3 0 min on a hot plate, adding water
tions, use a smaller sampl e and dilute t o to kee p th e volum e betwee n 2 5 an d
100 ml wit h water . Filte r th e sampl e if 100 ml. Alternatively , hea t th e solutio n
turbid. for 1 0 min i n a n autoclav e o r pressur e
(V) Ad d th e followin g reagent s i n th e cooker at 1 5 to 2 0 psig. Cool the solution
given orde r t o th e sample , mixin g afte r to about 7 5 F. Do not overchil l the solu-
each addition : 4 ml o f H 2SO4 solution, 4 tion. Dilut e th e solutio n to 10 4 ml with
ml o f ammonium molybdate solution, 10 water an d continu e as describe d in Sec-
tion 34(6) , beginnin g with th e additio n
drops (0. 5 ml ) o f SnCl 2 solution . Allo w
of ammoniu m molybdate solution.
exactly 1 0 min for color development.
(c) I f photometri c measuremen t i s t o Calculation
be made, determin e the colo r absorbance
of th e tes t sampl e a t 65 0 m/z, employing 35. Calculat e th e concentratio n o f
water a s th e referenc e solution . Recor d phosphate, i n part s pe r millio n P0 4, a s
the phosphat e concentratio n indicate d follows:
by th e calibratio n curv e prepared a s de-
scribed i n Sectio n 33 . I f visua l compari - Phosphate, ppm =
son i s to b e made (se e Note 8) , transfe r
50 ml of the sampl e solution to a Nessler Polyphosphate
tube an d compar e th e colo r o f the solu - = tota l phosphat e — or//bphosphate
tion with the colo r of 50 ml of the stand - where:
ard phosphat e solution s prepare d i n C = part s pe r millio n phosphat e io n
accordance wit h Sectio n 3 3 (a) an d (b) indicated by the matching standard
and containe d i n a serie s o f simila r or by th e calibration curve , and
Nessler tubes . Recor d th e concentratio n iS1 = milliliter s of sample used.
of th e standard solution that most nearly
matches th e sampl e solutio n in color. Precision and Accuracy
NOTE 8.—I f a commercia l color comparato r 36. Th e precisio n o f photometri c
is to be used, treat th e clea r sampl e a s directe d
in th e instruction s supplie d b y th e manufac - measurement i s about 0. 1 ppm o r 1 0 per
turer of the comparator, using the reagent s pro - cent of the result , whichever is the larger
vided wit h th e comparator . Mak e colo r com - numerical value . Th e precisio n wit h
parisons betwee n th e sampl e solutio n an d th e visual compariso n i s poorer an d depend s
permanent standard s wit h whic h th e compa - on the individual. The accuracy depends
rator i s equipped . Recor d th e phosphat e con -
centration a s directe d b y th e manufacture r o f on the apparatus and interferences in the
the comparator . sample.

14-21

Copyright by ASTM Int'l (all rights reserved); Tue Sep 11 13:20:34 EDT 2018
Downloaded/printed by
Escuela Politecnica Nacional (Escuela Politecnica Nacional) pursuant to License Agreement. No further reproductions authorized.