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JAPANESE INDUSTRIAL STANDARD

Testing Methods for

Water Content of Crude Oil
and Petroleum Products

Jrs K 2275 *

,. '" ', ,lo,,l

Translated and Published

by

Japanese Standards Association

 Teting Metho& for ( 2275 1S39
water content ol crude oil
and Permleum Pmducts

This Japanese Industrial standa.d specilies the methods ol quantltattve

detemination lor water content of crude oil and peboleu6 prcducts.

The g€neral matters for ihjs Standa.d shall be in acerdan€ wtth the

(l) The general matteG in common to Karl Fischer type volunetrjc titrimetric
method and v€.I Fische. type coulonetric til.imetric method shall be in
ac@rdance with JIS X 0113.
(2) rhe ronndjn8 oll ol numerical values shall be in accordance {lth
Jls z 3401.

(3) Sanpling shan be in accordance Nith the samplin8 method ol the second
sanple specilied jn JIs K 2251 or lhe method equivalent to it,

3. Classification of rdt Methods

The tst nethods shaU be classiiied into three methods 6 shom in

Applicable standaids, corepondjng lnternational standards and

Reference Standards: See pag€ 2?.
 classificarion ol Msth.ds ro Tesr rvdrer content

These are ,nappticab e ro rhe sampte

(1or e\amDle, asohalL emurs'.nr .on
rainrng additiv€s usabte ro emuhitv
or to stabilize lvater a0d oil.
lolatile and wei€r soluble subsrance
(lor ex!nple. .l.ohoh) is deternined

3, 'lh€ crude oil coniainitrg 150 mass

ppm or no.e ol totat of me..anr,n
sullu. and hydrosen srtride ca; nor

These arc ldbl€ to Lhc Derr.-

'nanp
l.um pr"du.G .onra'n ns addjt;\€s
with th€ subsrance (r) thereafr€r
reJerrFd to as an Lnterlenns strb
\rh(h eail\
r.acG $Lr I harl"ater.
FAch€r reJeent.
rr case of contajnina interlering
subsran.ej $h€n using ao erapo;a!_
rns apoaratus oi
hen, ol *hi.h the evlporared gas
does nor conrain an inre.fcrin'
subslance, may be tsted thrc;ah a
wateFcoDrenr evaFo.ating appararus.
lnterfering sdbstanc€s are as Ioll!Ns,
1l) F.ee alk6li, oridjzing subsran.e,.educins subsrance. subsraic€
-dnr'"",I'c $' .ooind s',' ds n6ridpar.
(2) Sull!. dioxide, subsrance reacting sfth pyridine or methanol io

when perbleum producrs containing water tess than 20 ppm! rhe nore
quantity of th€ sample nay be applied.
wl-' aate on -r' rl Lr .d rp.- s e r-0, r. p.efFr.btc ro.1o.)e
rl6 m6r\od o.oroi'g.. rtn 'r
or o,tj on i.rps'Fd \crF|o c1(
co" cr r.a ^iT .rr-rfF
o'.Jqd TlrFc-'-ot s'0s5.,.e,
Ih- -1r,8 e 'le o ocLFr.il g \a'Fr
.or.o- rFacrrci
content oJ 'oo ',,S
crude oil is appended in lnfornative Reterence lTesring
Merhod lor warer contenr in crud€ oil (R€acrbn Merhod with Hy:d.ide)l

Reference: One na$ ppm oi mercapran sultur and I mass ppm of hydrcgen
suliide in rhc sampte cause a losjtive erc. coiaspondin! to"0.3
mass ppm and 0.6 nass ppm ol lvaler respecrively.
 4.1 Outli.e of Testing Method Fui ihe sabpte in a distillalion flask, and
alter adding solvent insoluble in uater. reflux it whil€ heating, Condensed wat€r
and solvent will separate into tso layec afte. successively being t.6pped in a
wateFneasuring tube, and the solvent returns back in the disrilling flask and the
water stays in the graduated pa.t ol the tube, 'lhe sater content in the sample
shall be obtained frcm both the warer qlrntitl t.app€d in the tube and the nass
oi the weished-out sample,
warer conte.t -rester fo. Distitlalion llethod The tester is conposed oJ
(3t;;;A-FE:r.l,osa ai-; L bry

The insulating Ferlormance oi the tester shorld be a No or more when the

jmulatiry resistance b€tlveen th€ po\LeFsource terminal and the housing is measured
under closed circuit. ln the case oJ b€ing equipped Nith a lrealing cir.uit, 0.5 Mo

nig. l. water content rester used lor Distitlaiion ll€thod

(Shown for an Example)

(1) Distitljng Flask The distilling ilask as speciJied in Fig 33 oJ JIs K

The distilljns ltask sith 24l.r0 taper sround Joint h alailable too.

Renark When a solid or semisoiid specinen such as grease is tested' it

is allowable to use a separate type distiLLing flask, as shown in
FiA. 2. which is conlenient tor the op€ration both of $mpling
and of washing alter the test.
The ground glass butt loint beiween the cove. and llask shall
be uatertiAht.
 Fia, 2. separale Tvpe Distilling FLask (Shown lor an

(a) assembLy diasram (b) cove. lc)

{2) Coold The cooler as specjlied in Fig, 3J ol JIs ( 233c.

The cooler with lover taper oJ 2{/10 grouod joint is avaiLable too.
(3) waler Measurins Tube the water measuring rube as specilied in the
following (a) to (c).
ltbe lnp ro' .s rdde of rod€ lard glas'.
I4-"slnns
eqi'Dp{ Mit.re-sr'trt'br ar c\Pry o,o: m..r ^ale 'n'rvd on tle
sraduated place, and its shape and dimension are shoNn in Fig 3.

Fis, 3. 2-ml water Meouring Tub€

 5
K ?275-1939

l0 ml \ ater Mea.ur.ns -rbe T\e l0 m. wa.pr me"rrrn8 (br shdll

be rs.p-o1ed Fg,3 dt frg.37 oi Jl. x 2319,
'1 in Fjg. 4 is available too.
The tube shown

Fis, 4. l0 ml Wate. j\4easudns Tube

(c) 25 nl Wate. Measuring Tube 25-ml rvater measuring tube as specilied

i;FiE:-F6-;id-FE_35--lrs ( 233s.
The tube specilied in Fis, 5 is avajlable,

Remark The tube \u!h a cock at the lowest end oi the graduated part
ro drain collected Nate. may be avaitable, Fig. 6 shows the
scheheric diaEram of that tube.
Fig. 5. 25 nl water Meduring Water Mealring Tube with
a Ciock (Schenatic DiagEm)

4,3 Solvent rhe solvent containing no wate. is suitabte.

The examples of solvents sed according to the type of oil are
 (1) xr'..np , 1 ops .d \],r \pF f Po Jl. \ 243J or .! 3ro lF
'p
FEZirEd ,n rrs h 3r7r. 'e ' '
(2) Mixed solvent of Toluene-rylene Th€ toluene specified in JIS
-
K--863a ot tntr-i;i ume I No. I pu.e toluene specified in
( g
JIS 2435 and s0 lol ol xylene.
(r) 5olv4 I \d n.1 o' .od' dr nopl ld r r!
ap tr
, \.1'mdT;-€^ '
JLullare d -15"r "nd o o ime l or mor. o.L d e
'
at 160'c. and having a density (15'c) of 0.3546 g/cmtr or morc'
D': !!j! q!. r! ji $,1 r \ol F q" dsrill"rF o. s0
q
Do'line po.n .ec
ro - 'd 90 di. illa " or ll0'' ' ro\c-.
4.3.3 vorarile soirit solvent
Dc|o-L yq-n D' t'llJ'' rrrl \arroi Boil:T Po:.1 n -g'
J. r. Lar- ha\i1E d bo.l:'B ooi r ^:l r |rc ronc. 'tm

t2J lsooclane lsooctade ol 9s lolume * in pulity o. higher.

when it is diilicult to obtai( petroleum system dhtjllate
and the pet.oleum-systen distjllale oJ narrou boilng point
rangej the distillate! which has above mentioned boiling
point range and can b€ obatjned by the distillation of ihe
indust.ial gasoline sp€cilied in JIS K 2201, can be used

2. lsoociane specifj€d in JIS K 2230 can be serviceable

Table 2, Sotvent Usable According to 'rype oJ oil (Exampte)

Bituminous matte. lsuch

 3

4,,t The testins Drocedures for distillation m€thod shall

(l) Calibration of Tester whether th€ apparatuses are cofectly assembted

or not shall be confirned by the follow,ng operation: place clear
hydrocarbon oil and solvent jn a distilling llesk according to,l.b (l)i add
water accurately by the amount shoun in Table 3 using a buretre or
pipette and nix then well; carry out the operation given lron 4,5 (2) to
(5); and find the qmntity ol water collected, Il rhe quantity ot collected
water lalls jn the tolerance range speciJjed in Table 3, the assembljng of
lhe tester and othe. conditions a.e r€Aard€d as .orrect. If jt falts out
ol the rolerance Engej because such causes are rhought as rhe teakage
oL c"m. oo'dr 'arF
o -"dri,A,
m"c tr.r s ro-. ion olt.:d-, dnd
oJ the catib.ation shall be carried out aft€r rhe removal ol these causal

Table 3. folerance on calibr.tion .f ihe resier

water neasuring tubes

(2) Preparalion oi Sample Alter honogenizing the sample as shown in the

louowing prccess, prepare the sanple lor test,
sample is difficllt. carry orl two times or nore deasuring! and alerage
neasured values to determine rhe test result.

Mjx by shaking satisfactorily the sanple that is liquid,

mtx by shakjns after heatjng.
(b) In the case ol t.agit€ solid sadple (for exanple, asphalt), smash and
mix it satisla.torily-
4,5 llojglu|g of Test The procedures lor the test of distillation method shall

(t) weigh the sample NiLh 1l t accu.acy ol the sample quantity (r)
sFecified according to anticipated uater content into a distilling tlask as
shoon jn the followin8. and put glass beads o. zeolite to prevent bunping
 I
( 2275 1939

(a) Case ol Fluid Sample Take the sample using a neasuring cylinder in
tems oJ volume, Rjnse the cylinder fjBt with 50 nl solvent once. then
with 25 nl two times to remov€ the sticking sanple from the wall ol
the cylinde., and transfe. completely these washings jnto the distilling

(b) case of Solid o. Sticky Sanple rvcigh ihe sample directly into a
distillins flask, and add 100 ml
The quantity oI s.mple should prcfe.ably bc 200 ml or 200
g for the sample containine Lhe anticipated water content
les than 0.1 g, ard 100 ml or 100 g for the sample ol 0.1
ln the case ol the sample containing much waierj less
amount of the sample may be taken,
Renarkr Since the vapor of tolucne is harmful, be ca.eiul nor to
lihalc ir, Espe.ially, toluene is risky vhen it gets into the
eyes, and be car€lul in handling toluene as \eell as other

(2) clroose the water measudng rube 1 ) slrich is suitoble for the anticipated
water content in the sample. .ssembtc it tirmly as shosn in Fig. I Nith
special obserlatio. nor to let strean or liquid cs.ape iion Joints.
choose a \later neasrring lube pating altent@n to the

Case oJ Sampl€ Containiirg Distillate Not Higher fhan 100"C Such as

Crude Oil The tubet vhos€ uppermost graduation ljne is not exceeded
by the distillate ol not higher than 100'C, shoutd be choosed.
case oJ the sample Aboundjng in lvater content The tube. Nhose
uppernost graduation line h .ot exce€ded by the water couect€d, shoold
be chos€n. The cmploydent ol lhe lvater neasuring tube silh a cock.
ho$ever, shall be Jree of this limiaation.

Remark: The inside raU of a cooling tube and a sater measuring tube
shall be .lean enough lor condensed water to ilow doNn frcely
into a gradLated part,
(3) stuff cotton slightly in the lop oJ a cooler! and afrer passing water in
the jacket of the cooler! start heating the distilling flask.
(4) Adjust th€ heating oi the distitting fldsk so that tbe condensed ljquid lalls
at a rate of 2 to 5 dbps per second Jrom the loNer end oJ the cooler.
Continue the distiltation untjl no Nater is observed in any part other than
the ater measuring tube and the collected water 'tuaniity remains
unchanged for 5 minutes o. Iongcr.

Il .ings of sater sticking to the cool€r tube arc obseNed, either

increase the dislilling rate car€fully or stop the passinA oi cooling water
K 2275 t9a9

(5) lvhen ihe djstjlljng ol Nater ceases! allow the wate. measuring tube and
its @ntent to cool to roon tenperature. Transfer the wate. drops
sticking io the side uall ol the sater measuring tobe to the saterdrops
Nith a glas rod or by oth€r suitable means. Read the quantitt of th€
. ollr' rpd wd'F' 1 rre \J,c eas r' B I' bF
':r.
Note (:) Readins out should be madeat elery 0,1 ml for the case ol a
l0 nl or 2s nl uater neasuring tube, and at elery 0.05 dt for
ihe case oJ 2-ml tube.
4.6 cllculation and Result Calculat€ the waler content by ihe distillation
meihod ii;ffiE;i€ wir-F-dre rolrosiry rormula, and when water conient is 0.1
? or more, round oll the rcsult to one decinal place, and when less ttun 0.1 t.
round off the resulr at evert 0.05 t. Results shall be erpressed by votune * or

",'+t- ^
=#t
"/,=Y#
where, M: $ater cootpnt in sample (voldme X)

water cootent in sample (mass g)

quanttt ol .ollected Nater (ml) (For calcubring
ttii ml is supersed€d by g.)
quantity of sample taken (ml)
quantitt oJ sanple lakei (a)
density oi sanple (ls"c) (s/cmr),
.r.7 accuracy The accuracy on Nat€r ontent by djstillatlon nerhod shall
apply to the test results obtained when using lo-ml water neasuring tlbe and 25

F-o-dtdb.l.t \,\le" lSe dm! r"mp.-.s rFc.-o 2 rmer for

lr-.:hirqDr() d............'-s ie oJ rtF )am- pe6o1
',
the sane testing room, and on different days or at differot clock times,
th€ diit€r€nce b€twe€n the quantities ol collected water shall not exceed
lhe lolerance given in rabte 4,
(2) Accuracy on Reprcdrcibility The dilference between the t$o quantitjes
oi collected water obtained {h€n the same sanple is tested ea.h one time
lor the same qlantity ot sample with dillerent teste6, jn two dilferent
testing rooms by tuo dilJereni persons shall not €xceed th€ tolerance
giv€n in Table 4,
 ll

A.cdracy of D shllatLon Method

X2.l F$cher V.lum.tri. Tfir

5.1 outline of Testing Method After dissolving the sample in a mixed solution
in a ritration flask isolated from atnosphere, titrate jt lvth Xa.l Fhcher reagenr
which can reaci quantitativ€ly with water, and then detect el€ciri.ally ih€ point
Nhere the pol.rjzation voltage in titration system drops ab.uprly du€ to th€ iodine
liberoted. to lind the end poini oi titration,
'rhe Narer contenL in the sanple shall be calculated making use of the ralue
by mg (hereafler relerred to as ljter) by Nhjch I ml ol Karl Fischer reagent r€acts
Nith waterj lolume ol Karl Fisch€r rcagent consumed at titrationj and quantitt oJ
the ueished out sample,
rvater contenr Tester ol Karl Fischer volunetric Titrimerric i\4ethod Tlre
js@nd1.aror.
shows an example ol its assembly,

The insulalion perJornance ol the t€ster shall be s Mo or nore $hen the

insulating r€sistance betNeen the DoNe.{ource terninal and the case is m€asured
under closed cu.cuit. In the.ase.f being eqlipped with a h€ating circuit. it shall
 Content Tester (Example ol

inn;-iit

(L) Tilralion Flask The tilraliotr Jlask (r) is about 2s0-ml gtass-made flat
bottomed llask equipp€d Nith sample injection openjng, detecting
etectrodes, a nozzte lor titrari.n, and a drying tube (r)j and is put on
a masnetic stnrer caDable ol adiustins suitably the rale ol stirrins,
-rhe sample jntection opening shall be
around to b€ able to li1 with a
stainless*teel made or ethylene tetrafluorid€ resin nade stopper with a

Notes (6) All joints between glasss.re nust be ground and protected
owing to applying grease (uhich is nol reaclive Njth or
dissolved in Xsrl Fische. reasent).

(J) Such desiccatinA agent as dried sjljca g€l or active alumina

is put in order to p.event the mohtu.e absoption lrom

Remark: lvhen the sample is int.oduced jnto a tjtration llask by using a

syringe. it is advisable to attach a stopD€r shown in Fig. 3 at
the sample jnj€ction op€ning to Dr€rent the absoetion ol
mohiure lrcm atmosphc.e-
 t3

Fig, 3. Stopper (Example)

{StainLess-steel or ethylene tetraftuoride resin made)

\2) Burette The burette with a scale inte al ol not morc than
0-5t;I.
In the case oi an autonatic burette, a l0 ml or 20 ml pislon bur€tle,
eqllpped sith an automatic switch valve. whose mininum discharge snount
is contrclled by a pulse motor to be 0,01 to0.02
(3) Sampler The sampler shall be abl€ to tak€ the sample without receiving
;nv-Ffluence sNen bv outer air "ater content,

FiA. 9. Sanpler (Shown for Example)

(t) t2)

!t
4.:c
r =is

Y
EvaEorator ol Water
The evaForator of sater h.s a
a6nairuaibiil-fiT6duce the water vapor! which has been
vaporized by means ol sater-frce nitrogen gas and the llke fron
the saftple shile heating, into a titration flask. and Fig, l0
rhh apparatus shall be handled according to the attached
 l4

Flowcharr oJ $arer Evaporaro. lElample)

R.dae ro o, -d fo. h"r i ( !r \ollme r - d nneur

method str Iff s r.ll.wr
(l) Karl Fischer Reagenr according to the anricip.tei rvater in the sample,
ch@se suitable one among 0.5, t.0,3.0 or 5,0 mgHro/mt of riier,

This .eagent shalt be kept in I dark and cold place $ith shietdjnA the

Remark Karl Fische! reagent shall b€ prepared in accordanc€ with the

nethod speciJ,ed in JIS X 0113,
(2) Mixed sotvent Either a mixture oJ one lolume ot merhanot dehyd.at€d
in accordance lvith JIS X 0tl3 and 4 vohnes ol chlorcforn specitied id
JIS X 3322, or ant oth€. mixed solrent suitable to rhe sanple.
(3) Water-methanol Standa.d solution lts titer is

Relerence: The water nethanol standard solution for (arl Fischer

re.gent! which is on the narket, may be used,
Reoa.k: Wh€n organic solvent is !sed, avoid inhaling fts vapor, and wash
with soap and Nater il it adheres to the skin.

s.a qgpaJatjon ol Test rhe preparation fo. tesr ol Karl Fischer votumetric
titrinetric melhod shall be as folloNs.

5.c.1 Standardization of Titer of sarl Fischer Reagent Prior to the test,

rhe titer or I;ii-TE;i;;@nt sfiell Se steirifizedircordance with rhe
(l) Method usjng water
la) Place about 50 ml mired sohent in 6 tit.ation flask. and after
stopperinAj run the naAnetic stirrer. Then- st3d tit.,tion uiih (erl
Fischer reagent, and get an end point (3) to make the lnside ot the

Not€ lr) The end point shall be the moment {hen the abrupt dbp
. ol polarization voltage. caused by one drop of l(arl Fischer
reagent, has .ontinued lor a delinite interval (fron 30 to
 K 2275 1949

Renark: lvhen the solution has been leJt for the time needed Jor
test alter the inside of the titration f lask b€comes
water-ire.j retitrat€ it, and
.eagent is not consumed.
(b) Then intrcduce quickly water ol quantity specified in Table 5 into the
tjtration llask using a microsyrince l!), The lolune of water shal1
be precisely measured to the iearest 0,1 mg oNing to the Noight
difl€r€nce ol th€ syn.ge beiore and after i(t.oducin8 saler.
The stopper should be kept open as short as possibl€ !n
order to pr€venl ihe absorption of water lrom atmosphere,
Tdble 5. qdantit' of wster to Be Talen

(c) Titrate again to th€ end point (3) by the meihod sp€cified in (a)i and
read the quantily oi Ka.l Fischer reagent consuned ior titration to

(d) Calculate the titer ol Karl Fischer reagenl to thlee signiiicant figures
by the lse of ihe lollosing formula:
4,
li
Karl Fischer .eagent (mgHro/ml)

{: quaotjty of Karl Fischer reagent consuned fo.

{2) Method Usins water-melhaool Sbndard solution

(a) Make the inside of the tibation llask Nat€r lree sjmjlady to the
method speciried in (1) (a).
(b) Drop water-methanol standard solution ol the quantity given in Table
6 from a buretle to th€ titration flask. and read the quadtity dropped
to the nearest 0.01 ml,
 T"blc 6. Qra irj or \\ar-r'e' d'ol crdnoord soht.o. o Bp td--'

Quanlity of water methanol

standard soluii.i nl

(c) Then titrate again to the end Foint (3) sith Carl Fischer r€gent, and
read the quantity of Karl Fischer reaaenr consumed tor titration ro
the nearest 0,01 ml.
(d) calcriate the tjter of Karl Fischer reagent Nith rolnding otf to three
signiljcant ligures by th€ Lse of the folloNjns tormuta:

titer ol turl Fjscher reagent (mCH?O/mt)

titer oJ water-methanol standard solurion

quantitt ol sater-methanol slandard solution {ml)

u quantity of Karl Fischer reagent consuoed for

Since the tter ol warer-merhanol srandard soturion

changes because of noistu.e absorptjon Jrom the
atomosphere during storage! it shall be vedfied by
a Karl Fischer reagent, which has been iitrared by
water-lsing-method! when jt
is not used for a long
r.4,2 Prada.aL on
,,t,eq.- Lo= =a:::n-.ro.r-rr J .d o"ins."ms
",i b.

{l) Sanple container shatt be ot sttucrue capabte ot seating hermerically

and be used after Drevjously dried.
(2) The quantity of saEple to be taken shall be at least 30 percent ol a

(3) Alter sanpljng, it shall not be transferred into another conrainer.

 l< 2275 1939

t4) sample shall be homo8enized owing to saljslaciory mixing by shaking ol

the contain€r before opening.
(5) sample container shall be opened aller s.mple tempeEture has become
rcom temperature,
(6J Test shall be caried oul as sootr as the contaiier is opened,

5,5 Test Proc€dures The prd.edrres of (drl Fisclrer rolumetri. riLrim€fti.

ner h.d cI;iI na;-i6lrNs.
(l) Mesure r00 ml of mixed sollenl in a iitration tlask, and operat€ tbe
masn€iic stir.er with the stoppe. on. 'lhen siari iitration, atrd titrate to
rhe end poinr (r) Nith (arl Fhch$ re.getrt so as to make the inierio.
rlask u3reFlree.
(2) Using a sanpler which has prelinintr,ly bccn dned at aboui lto'c for one
hour or longer and then has been cooled in a desiccato. cotrtaiDing silica
geL or rh€ like. take a sample by.cfe.cncc to Table ?, atrd.dd it
pronptly id th€ titration llasl( ( ).
Obtain the qranlity of sample by neasuring to lhe nearest 0.01 g using
the dillerence jn mass of thc sampler benveen belore .id afier addition

rrble 7. auanritr of )?mde ro 3e rckE

Antjcipat€d rat€r jPe ol r\arl lrscher reaCent il ten

content

Over 1000 up !o and inct. 10000

lvhe.e lsins a.syrinse for sanpling. d.aN in a sanple oi a quadtity

up to about il of ihe capacity ol the syrinse to preveot the
leaking jn ol air through lhe ground glass slidin8 surlace ol the
syringe. Then dlter removing air bubbles by dir€cting the syringe
needle upward, insert the tiD oi the syringe ne€dle itrlo a silicon€
rubber prece, and aJter w€iting the ground-glass sljdnrg surlace of
the sy.inge {ith the samDlc by applying Fressure. disca.d the sanple.
Alter repeating thh p.ocedure llvo or three times. draw the sanple
sloNly into the syrnrge.
When weighing the syringe. make it with the silicone rubber piece
attached to sy.inge, then alter removing the silicone rubber pi€ce
and placing the sanple jn the tit.ation ilask, welgh the syringe aga'n
'with th€ same silicone rubber piece as used beJore, and take the
dilferencc in mass belore and afte. adding the sample as the
 t3

when, in the c6e ol crude oil test, the quanrity ol the sanpte
exceeds L3 g or that ol th€ Karl Fische. reaSent exceeds 23 ml
.elative to 100 g ol mixed solvent in rhe titration flaskj the
incomplete dissolutjon oI rhe sample in the sohent oay bring an
inaccurate result. and so the conlent ol the flask shatt be reDlac€d.
(3) Tit.ate again to the €nd pojnt itr rhe sam€ way s that in lt), and read
the quantity of Xarl Fjscher reagent consumed lor titration to ihe nearest

5.6 Calculahon and Expressjon ol Result calculare the water content by (art
Fischer volumetric tibimetric qethod in accordance with the follouing tormula. snd
in the case of crude oil! round oll the volume g or mass * up to three si8niticant
Iigtrps rDrov dFd ac. .hd ralldsr s'g'i i.d'.081.1"..0".:oppFd dr r,e -!o1o
,le!in"l poinr). l' caie o od.o..' r rodr.r.. or'd o.. np \oturF pp- o,
mass ppm up to three'\Fsignilicait figures (provided that the p?rr smaller than
d€cimal point shall be rounded to an interger).

w%=+i[ Aa '. w"%=.yif\n ,

'/--=#,,"
waler .ontent io samDle (volune *)
waler content in sample (mass *)

Fischer reasent consumed lor

tite. ol Karl Fhcher reagent (ngll,O/ml)

quantity oJ sample taken (s)

density or sample (rs'c) {s/cm i),

The accuracy oJ Xarl Fischer volumetric tftrimet.jc method
tlral this accuracy shall apply to the crude oil ranging
be ;-T;roy-onos. provided
water! and to ihe petroleum products ransins lrom 30 to 1000

{t) Accuracy on Repeatability when rhe same person has tesred the sane
sampLe tNo times wjth the sane tester in the same testins mon on
dr(l"r"n. o"J or d' l- d rfFr.n F in rcs; rsu. s .\d
noi exce€d the toterance given in Table 3,

(2) Accuracy on Reprcducibility The diJlerence b€tween the tso test results
obtained when two diffe.ent pesons have lested the same sample each
one tjme by dillerent testes in two dillerent testing .ooms shall not
exceed ihe tole.ance siven in Table 3.
 F: averase vahe ol tesr results lvol * or mass
r,: av€rage vdlue ol t€sr resutts
(vol ppm or nass ppn).

6.

6,1 outline of Testinq Method PLI the sample in lhe anode room ol an
electrolyii*-iT-61lGi--nr atmsphere. cen€rate iodine by elecirolysh rrcm the
(arl Fischer reagent in which iodide ion is mixed instead ol iodine. Obtain the
qlantity of water lron th€ quantity of €lect.icity consumed to generate iodine
makins use ol the quantitative reaction between rater in the sanpte and this
iodine. calculate the water conLenl in the sample from both the quantity of Nate.
and thal oi the sample,

6.2 Water-content Tester ol l(arl Fischer coulom€tric Titrimetric Method The

k${,,ffiF,. jts
a detector. an indicator, etc. Fie, lL shoss an exadFle oJ assemblins.

The insulating perlormance of lhe teste. shall be 5 Mo or more $hen the

insulating resistance betN€en the poNe. sou.ce teminal and the case is measured
under clGed circuit. In the €se ol being equipped Nith an etechic heatjng
circuil. it shall b€ 0.5 Moor more.
20

Construction of water Content Tester

(Example oJ coulonet.ic Tjtrimetric j\4ethod)

Remark The quantity ol wat€r (rA) sh.ll be indicared on the indicator,

l1) ElectrolysisCell Th6 cett is about 200 nl .aFa.rty gtass cell and
compos€d ol an anode chabber and cathode chamber, both ot which are
separaied by a diaphragm such ion exchange membrane, and
the sahple injection opening is equipped wiih a srainless-sreel nade or
ethylene-telraflloride made stoDper. 'lhe c€ll is exehplified in Fig, 12,
The openings of the €lectrclysh ceU, Nhlch lead to atmosphere, shall
be equipped sith a dryjng tub€ containing desiccaiing agenr ot snica gel,
and the joints between glassware b€ ground and applied with grease (thai
Nhich does not react with IGrl Fhcher reagenr nor is dissotve! shall be
used) to prevent the absorption of moisture from arnosphere.
 Fie. 12. Elecliolysis Cell lExample)

la) Elect.olysis cell (Insid€ (b) Elecrrolysis cetl (ourside

cathode chamber Type) Cathode Chamber lype)

(9 sanpre hlerior o@^ig

(c) Entarged

(Stainless st€el made or ethllene-tetraf luoride made)

S gl.::l-"-""""''
Wtr
 exenplified in Fig. 13.

Fis. 13. sydns€ (Exanple)

Remark Evaporator ot \rater The evaporator of water has a

constructjon to rntbducc the waier vaport whi.h has been
vapodzed by meaDs ol water-free nit.ogen gas fron the sample
shite he.ting. inio an electrolysis cell! and nig. 14 shows ts
This apparatus shall be handted according to the instruction

Fig. 14. FloNcbart ol water EvapoGto. (Example)

6.3 Reagents Reagents to bc used fo. Karl tischer coutometic ti$imefic

(r) !ls9!I9[!:a&!]!19! rhe rollowinc electrotvtic soltrtidis ..e

(a) solution lor Anode Mixed solution composed ol iodide ionsj
dioxjde, electrotyte slch as pyridine or alt€rnative base, and

(b) Solution lor cathode nired solulioo composed of iodide ions, sutfur
dioxide. €lectrolyte srch as pyridine or alte.natile base, and organic

Reference: The composition ol the electrolyte solution is exenpljfied

in JIs c 2l0l and JIs K 0l13.
(2) Wate. methanol Solution Add sat€r in 2 methoxvetharcl so as to hake
r-]-o-l-rF mrrrur"i' ooo' 4 ns o sa'-r.
 Renarks r. Electblyric solltio. aod wate, melhanol solutioi on the
narket may be !sed.
2, when o.ganic solvent is used, avord absoiltion of its vaporj
and sash wjth soap and water il it adheres to peEonat body.

6,4 Preparation ol T€st Thc calibration of the tester sed in Karl Fischer
hethod sha11 bc .arriod

(l) Place about 100 ml anodc solution in the

ele.trolysis cetl. rhicb has been cleaned and dried, and about 5 ml
cathode solution in the cathode chamber, and mount the assembled

(2) while mixing by agitaring the anode solution in the elecrrclysis cetl. tloN
the electric current for electrolysis (t:). and neke the inside of the
electrclysis cell water-iree orving to the production ol iodine a1 anode

(31 Then iniroduce accuratcly 5 I ol waler into anode solution using a

ni*osyriige, and obtaio water cootent by carrying out coulometric
uhatton !o get an end poin!. Reoeat t{o times or mo.e this procedLre,
and the Nater content obtained shall be in rhe range of 5000 1 250 !g.

Noie (',) As lona as liberated iodine €xists in anode solution,

elect.oltsls 6 not carrjed oui, I0 such case, it is
preferable to add excessilety wateFmethanol solutjon or
water by the quaniity corresponding to 2000 to 3000 lgHro.
{r.4,2 Pr-pardrioo o( camp." B- a'r- l.c \dnp.- g- pas"v
frco aLro-5p€-,rrefolro"'Rre '5\rll b- drnd doo'r, 'F 'fl'-r..
(l) Sample container shall be ol structure capable ol s€aling hernetically
and be used alter previously drying.

(2) The quantity ol sample to be taken shall be not les than 30 per.ent
ol a sample container.
(3) Alter sampling, it must not be transle..ed into another container.
(4) Sanple shall be honogenized owing to satisfacrory dixing by agitatioo
ol the container belore opening,
(5) Sample container shall be opercd atter sample temperature has become
room lemperature.

(6) Test shall be carried out on the sample container as soon as the
container is opened.
 6.5 Test Pro@dures rhe procedures of Xa.l Fischer coulometric titrimetric
method shall be as folloss.
(r) wdsl.inq tri I .ol'..or of S,1'qp -\r n rse )idll be $dshed nr.n thc
fi=iffiirc;--- " illo-"l-n- Dro -orr:.
(a) AJter previously washing and drying a sy.ing€ and n€edlej keep them in

(b) Take out the syringe and needle lron the desic€tor, and after
assembting themj lei th€ point oJ the needle pierce a rubber stopper.

(c) Renore the rubber stopper ol the syringe. ond after letting the needle
penetrate as deeply as possible fron sample suriace! draw the piston
ol th€ syringe to suck the sampl€ up to lhe naximum graduation or

Renove the stringe lrod the sanple @ntainer! and discharge the sanple
aJter dra{ing ort air wiLh keeping rhe needte up$ard. Repeat thjs
uashing with solutjon procedure at least hvo times, and confirm that
there .enains no air bubblc insid€ rhe syring€.
rp oddr io hc
capacity ol the sy.inge io prevent the leaking in ol en
through the ground Alass sliding surtace of the syringe. Then
after rcmoving air bubbles by directing the syringe needle
upNard. insert the tip ol rhe syringe needle into a rubber
piece, and afte. weiting the groud-glass sliding surface of
the sy.inge rvith th€ sample by applying presure, discard the
sanple. After repeatjng this procedure two or thr€e times,
begin the procedrre ol (c).
(l) After taking the sample in the syriDg€ by 0.1 to L0 nl (r) according to
the anticipated quantity ol Nateri seal closely the tip oI the needle with
rubber stopp€., and lvejgh its hass to rrre nearest 0.1 mg-
Not€ ('3) The standard oJ th€ sample mass to b€ taken Nhjch is
inlluenced bl anti.ipated sare. content is shown in
Fig. r5.
Fis. 15, Quanrity oJ sampl€ to Be Taken

F;30

ir;i 3A
 25
x 2275-1939

(3) Next. injecr the sample kepr in the syringe thrcu3h a stopper into anod€
solutjon in the tibatjon Jlask lhich has been dehydrated belo.ehand,
(4) Seal closely aeain the tip ol ihe needle sjth rrbber stopper, and {ejgh
its nass to the nea4st 0.1 mg, Obtain the nass ol the sample. uhich
Nas iojected. Jrcm the mass difler€n.e ol the syringe befo.e and afte.

(5) Titrate coulometicalll ihe wat€r cont€Dt in andde soldlidn to gel a end
pojnt, and .€cord th€ quantity of water (!g),

6.6 cal.utation and Resrlls calculale the ,te. cont€ni

io'lo-prn. n-rlod'r d.oddr'ru. rrF fo,.\''elo'nr". o ' 'lc
case of crude"rn6r
oilj round ofl th€ volume * or inass * Lnit uD to lhree sisnilicanl
fiAures lprolided that the smallesi significant digit shall be the two places of
decimats). ln lhe case .J Fetroleun products, round olf the lolume ppm or mass
ppm up to three significant ligures (prolided thaL the part small€. than decinal
Foint shall be rcunded olf to an interser),

w.%=+;xN ' wt/o=+tb.

t;;ao" !2
'v.',t.-
waler conrenl ii s.mplc lloluEe *)
lvai€r contcot in sample (nass t)

qdant[y ol water (ag)

quantity ol water (!t)

quanrily ol sadpte takeo (g)

densitv ol sample (15"c) (s/cmr).

6.7 Accuracy The accuracy of Karl Fischer coulomeiric titimetric merrod

shall be as follous, p.ovid€d that th6 acclracy appli€s io the crude oil ranging
frcm 0,02 ro 2 * of w!te.. dnd to Lhe pelrcleun product ranging lbm 30 lo 1000

(l) A..ura.y on RepedldLililv whe' the sa,ne peD!n

a;;l-F r*. rh.'-urh irP <
diff;rent dars or at dillerent iimes. the dillerence
not exceed the tolerancc givco in 'rabG e,

12) Acclracv on Reproducibilitv The dillerence b€tween ih€ lwo test resutts
6It-ainedwhen iwo dirrereni persons have tested the same sample ea.h
one time by diffe.ent testeb in lwo diJfe.ent testing rooms shall not
exceed the tolerance sjven in lsble 9.
alerage vahe of lest results (vol I or eass g)
average valle of test r€sults
(vol ppn or nass pDm),
 JIS K 0ll3 ceneral Rules lor Methods of
and coulometric litrarions

JIS t( 2201-Casoline lor rndusrrial PrQose

JIS I{ 2251-MeLhod ol Srmplirg crud€ oil and Petroteum Producls
lls K 2230 Testing Nlethods fo. Octane Number and cetane Number
(Benzene loluence . Xytene Solveni naphtha)
IIS K 2339-Classwa.e for Testlng Apparatus ol P€troleum Prcducls

JIS K 3271 xylene

JIS K 3322-chlorolorn
Jls K 36301oluene

JIS Z 3401-Rutes lor Rounding off ot Numerical Values

corresponding Intemational siandardsi

ISO 3733 Petrcleum products and biiuminous nateriah Dete.mination of

vate. Distillalion method
ISO/DIs 6296 Liquid petrcleum producis-D€terminaiion ol NaterKa.l Fh.her
nethod

JIS C 2l0l-resting ltethods of Electdcal lnsulaiing Oils

JIS K 2203 Kercsine
JIS K 2423-Methods for Testjng Pyridine Bas€s

ISO 9029 crude petroleum Det€mioation oi uater-Dhtillation nerhod

lso/Dls 9114 Petroleum p@ducts-crude oil-Deternination oJ water content

by hydride reaction
ASTM D 437? Standard Test Method lor Water in Crude Oils lxarl Fischer)
 2A

Inlormativ€ Ref ercn.e. TestinA Method ior Warer contenr in Crude Ojl
(Reactjon Merhod sith Hydride)

This rnJornatile Relerence specilies the neihod to neasure water content.

^l'c1 i!,on drFd floc oit r' .t- rd-ge i'on O.O" o 2.0 \olump t, oJ m-dn
oJ rea.i on mFih..l "u'rh hvdridP

Remark This nethod is suited ior measuremen! at the site orher rhan a
laboratory because ol a portable type and no need of electricity or

2, Outline of Testins Method

Place 20 ml sample in a reaction flask, and after adding caloum hydride,

colleci in a gas burette the hydrogen 3as whi.h gen€rates osing to rhe reaction
01 $ater in lhe sample and calcium hydride. oblain the warer content jn the
sample by reading the graduation ol gas burette (convert€d to lolume I ol lvater
.onteni). showins the volumc oI hydrogen Sasi scaled on the gas burette

3. wlter content Tester ol lrydride Reacrion Method

The teste. is composed ol (r) to l4)j and Infornalive Reterence Fig. I shoNs
an example ol its assemblins,

lnformatne Feference rLg, I Water content Tester ol Hydride

o
o
o
o

(t) 100-ml llask wtth three mark€d lines corresponding to t0

ni;-2d-rt. and-
 29

{2) Cock lor Reagenr charging Fi[ed sith an opening for holdi.g ihe capsul€
containing cal.iun hydride and for .harging 1t into the reaction flask by

cas Burette and water Leveling Bulb These are cohposed

flat boitomed cylindedcal gas burett€ and a wat€rleveling
regulationj aod ihe gas burctre is gradDat€d lmm 0.00 to l

This graduation shatl hare 1,00 X graduated liDe Nhjch shoNs the volume
ol htdrog€n gas (20'c, 101.3 kPa) g€nerared by rhe rea.rion ber$€en
calcium hydride and ll0 ml sample containins 1.00 volume * of sare., on the
refc.en.:e ol 0-00 X lin..
'llre threervay cock capable ol slvitching th€ gas channels
rlask, l.ec atmosDhcre, etc. o\ring to its roiatio(.
Remark other measrremeot m€tlrods than the case ol a gas bur€tte may
be available to measu.c hydroaen qas vol|n'e.

The reasents fo! htrd.ide reaclron method shall bc as follolvs.

Capsule lor Reagent Powdery calcium hydride ol 0.6 to 0.7 g is put in a

caDsute Nhose siz€ suits lor the oDenins ol a reasent holdins cock.

(2) Reaction Promoter 'rhe reacrion pronoror caoable oi Oronoting rhe

re.ction between Nater and calcnLn htdride, and sodium dioctyl succjnate

Remark: The cap rle for reagent and .eaction p.oEoter! both dJ lhich are
rlie .ccessory of rhc Gsrer ol hydride reaction
mctbod, can Le coileniently used.

13) piluent Keroseo€ specified in JIS K 2203 or hydrccarbon containing no

i1 shall be confimed that the Nater cont€nt test on ,10

nl dituenr siles less than 0,01 volume t ol water.

5,

5.1Pr€par9ljgl glI!!!q For the purpose to carry olt accrrarely

neasurement according to lhe hydride reaction method, il is inportant to ke€p all
parts hermetic by close cotrtacL and the reaction flask clean.

The.efore. the follounrs shall b€ duly checked.

(t) aJter washing the rcaction llask sjlh solvent Guch as heptane or
acetone)! eiihcr dry n Nith dried air or oipe Grelully $iilr gauze or
 (2) Check ihe condjtion of dirtiness and votune oI the liquid {gas oil
containing no oateo kept in the aas bu.ette, and ,i necessaryj change or
supplement it.

(3) Coniim the airtightness ol a tesler system {hereafter referred to as

5.2 Prepa.ation ol Sanpl€ Make the sanple homogeneous by the following.

and prep:re the sampl€ Jor neasurement.
(l) Mix by shaking satisfactorily liqujd sanple,
(2) In the case oI high Fou. pojnt sanplej iJ necessary! hear and nix by

The Drccedures of hyd.jde .eaction method shall be .s fotlows:

(l) Place the sample. whose quantity (r) is given in Infomative Reterence Tabte
ac@.ding to the anticjpated water jn the saople. in a reaction llask up ro
the narked tine. In the case ol high viscosity of thc sanple, add diluent.
prcvided thar total of rh€ sample and diluent shall not exceed 40 ml.

Note (r) \lhen anti.ipated water is unknown, put the sampte to the marked
tine ol 20 ml.
Info.marive Rcrcren.c T.hlF Qdahtity ol Sample ro Be raken

Antic pated warer conrent ivo i)

1.0 or dver to and ex.l. 2-0

Ren.rk when the sample is to be tak€n by mass, the nass appioximately

correspondjng to votuoe shall be judg€d according to anticipat€d

(2) Afte. adding 3 drops of reaction pronoter in a reaction ilask (,). atrach rhe
cock for reagent chargjng to the flask.
Note (:) In the case of agitating using an electromagnetic slirrd, put an
ethytene-tetraJluoride covered .otor in th€ reactjon flask,
(3) After having adjusted the liquid level (lower edge ol neniscus) to
0.00 I li(e, make the condition oi the systen closed.
 31
K 2275-1939

(4) Shake the reaction flask to remove volatile matter in the sample (r) while
cafyine out this prcc€dure, obseNe ihe height ol the level in the gas
bureite. and if lhe lluctration oi the t€vel is reo$ized. make olten the
three way cock 'open' in the systeh lhlormative Reierenc€ Ftg. 2 (A)l to
lc. oi. hdree vo al c
rdnovar op-rario' Lnril rc ''d.
'a
id o( Lquid _.F j1' gdc bFlrc i<
'
Note (r) It an elcclromagnet,c slrrer is 6en, carry out the agitation of

Intormatjve RefercncP Fig. 2,

(c) Open'Position rn lhe system lBl 'closed' Fositjon in the System

- l. \.,,
,', :,
ll

(5) After the completjon oi the operation to remove volatile natte., set the
three-way cock at lhe position'closed'in the systen, and make the liquid
lelel (lo;er edge oi meniscus) in the gas burette coincide with the
graduation oJ 0.OO g by adjusiing the liquid level of the lereling bulb

lbJ DerdLh rhe ldD of a r-a!-1r '. \r opp 'C br I' i13
ro. ie"ee'€!rr RFfF o norr J"vc R't''el F
're. I ra,l, afrc- ndre"erl' 'dgFi 'apd6 nrl'rldkotrtr3ro
o""...R 'i" rc'" ." ( io: ""8'F i.rgre. "L' '
 Informaitjle Reterence Fig. 3. cock lor Reagent Charging

{A) Position Holding the Reagent (B) Position cha.ging rhe Feasent

-/ ff:J,::'* " *"

Note (r) \latdial not Demeable bl

tetralluorjde or hldrogen,

Mix by shahng Aenrly the reaction llask to ler bubbtes sligh y evotve (3).
'rhen nix by shaking gradualty and strongly while observrnS ihe condition ol

Remark: ln the cas€ ol a large amounl of war€r conrenr in the sampte ?nd
too liolent stirring! the conrenb ot rhe ltask may ilos olt oNrng
to the Aeneration ot a lot ot bubbtes. In such case, cease the -
test and rehy the t€sr atter making rhe qrantity ol the sampte
smaller (about h.lt ot the original).
(3) When.bubbling has finished and tiquid level in rhe gas buretre has again
siabilized! stop mixing by shakina, Adjust the tiquid tev€t jn the
waterleveling bulb to coincide with rhe tiquid tevel (tower €dge of
meniscus) in the gas bu.etr€. and read the graduation of rhe buretre,

(9) Tak€ off the cock Jor reagent chargins from the reaction ltask. and atter
adding.s.ml or more merhanol and recqoizing no bubbling (hydbgen).
discard the cont€nts in rhe flask.
Remark Not-yer-reacted cal.irn hyddde b€cones catcium hydroxide ait€r
r€aciing sith methanol.
?- calcnl.tion and Resulis
Calculate the water entent by hydrid€-reacdon Dethod in accordance wjth
,rr" r"I.*'"":"it,'". ad rcdnd oii iiF rPsulr to L{o sisn l.carr risrles {D'ovo'd
rhdt r5e 6m;ler sjgn fr.alr digi. ,rall bP L 'e r*o Dla(es o' d'cirdlr'
w=4+
wheret r. sater content (volune *)
s: quantily of s.nple taken (ml)
v.. rading on the gas burette Nhen s.mple is te6ted
(8).

Remarks l. When sadple is taken bt nas, calcutate ac@rding to the

fouowing formula.

where. r. water content (volune t)

quantity ol sample taken (g)

deNity of sample (20'c) (g/cm3)

v' readlng on sas burette shen tested (8).

2. when tested under special metorclogical condition (temperatu.e

rte
and oressurcr, "at"u,"te a corrP'rion facror usi
"tmosotPric
lol,o ing iorula. ald nL lrplv ne test rPsL bv rhis 'c
ta'Lor'

.,=inB-tE t+1i:6il

where, l: correction factor

?: atnoshedc Pressu.e (kPa)
r: temPerature ('c).
 \

Erlsbt+ed by Mm$rer o ,nr.'na'bnal Trade and i-d6r-y

Date of Establishmdi 1954-07-20

Dare of Revision: 193$03 0l

Date or Publlc Noti@ in ofllclal cazette; t939-03-03

lnvdgard by: JoDre!€ lnd6mel slandeds ronmlttee

Drvsiona. coun.tl on NatuEi {6ou cet
and Enersy

I
Thk English transhnon l. publbhed bt:
Japsnese standards Ascjatlon
l-24. Akasaka !, Minato-ku,
107 Japoi
"olqo
@ JSA,lt9o