VOL.

ANALYTICA

(1948)

COLORIMETRIC

I-I. A.
Cmltrd

CtiIMICA ACTA

DETERMINATION

J. PIETERS,

OF

XV. J. HANSSEN,

I_abornlor_v of the Nelhcrlands

SIafe

241'

AND

Coal

MAGNESIUM

J. J. CEURTS

Manes,

Gcfeen

(Nellrcrlamfs)

INTRODUCTION
When magnesium hydroxide is precipitated in a solution containing titan yellow,
the precipitate is coloured by adsorption of the dye. When the solution contains
a protecting
colloid the magnesium hydroxide
remains in the colloidal state,
retaining the ability of adsorption of the dye.
Under the proper conditions the intensity of the . orange colour of the solution
is a measure of the magnesium content.
GINSBERGI uses a I %s starch solution in dilutedglycerol
as the protecting colloid,
an excess of titan yellow and light of 546 rnp from a mercury lamp. SINIGAGLIA~
does not use an excess of titan yellow. LUDWIG AND JOHNSON~use starch and light
Of 523 In/.&.
The procedures described in the literature I-g differ only in the composition
and the quantity of the reagents. As they are developed for the determination
of Mg in water, they practically do not contain data on interfering substances.
In an attempt to develop a satisfactory procedure to determine Mg-+ in water
and in silicates we studied the influence of the following factors usbIg a Lcifo
photometer.
I. Wave-length
of the light
a
2. Stability of the solutions
3. Quantities of the reagents
4. Extinction
as a function of the concentrations
of magnesium and of titan
yellow
5. Influence of Ca, Fe, Al, NH,c! and other electrolytes.
The results are presented in graphs and tables. We devised a procedure which
enables us to determine quantities up to 2 mg of Mg with an accuracy of 0.02 mg.
The procedure is relatively simple and saves us a lot of time. The accuracy is
greater than that of the gravimetric method.
Iron and aluminium interfere, Ca and alkali-chlorides
dont. The method was
adapted to the analyses of water and of silicates.
Re$erences

16

$. 253.

H. A. J. PIETERS, W. J, HANSSEN,

242

VOL.

J. J. GEURTS

2 (1948)

RESULTS

The wave-length which gives optimal

We used this light in our dctcrminations.
I.

FIN. x. Absorption

spectrum

results proved

of solul~ons wth

to be 534 mp (Fig.

and wthout

IQ

2. A solution of starch in water does not give satisfactory

stability
Better results arc obtained with a starch solution containing glycerollo.

0 5ooo

Fig.

2.

60

120

I).

(Fig.

2).

I80
(mmn_l

The cxtlnctlon cocIliclcnt as a function of the tlmc, after adding

different quantities
01 I ;& st,lrch solution, wh~lc the Rig-content IS kept constant.

VOL.

2 (1948)

COLORIMETRIC

DETERMINATION

OF

143

MAGNESIUM

Fig. 3 summarizes the results obtained with solutions containing starch and
glycerol in varying proportions.
Gelatine and gummi arabicum are unsuitable as protecting colloids (Fig. 4).
We recommend a mixture of IO ml 2 %s starch solution and IO ml glycerol which
gives reproducible results after 40 minutes. The colour does not fade during 3 hours
(Fig. 3). Small variations of the quantities of starch and glycerol arc of no importance.
3. The quantity of sodium hydroxide added to the solution influences the results
and conscqucntly has to be kept constant (Table I). \Vc recommend 10.0 ml 2.0 N
sodium hydroxide.
ThBLIZ
INPLUICNCE

Optlmi1I

ahorptwn

01

SMALL

\ARIATIONS

at wave-length

IN

534 mp

I
TIIC

wlicn

C;L+~ >

TABLE
REQUIRED

QUANTITIES

x0

Or

TllC

\OLUl-IONS

mg

II

QUANTITICS

Ol-

x mg RI&

:I

0.0

TITAN

YRLLOXV

mg titan

0.G

2.4
3.6

12

.I.8

r.8

yellow

G.o

I
4. Fig. 5 gives the extinction
(Big bcmg kept constant).
Rcfevemxs

p. 253.

as a function of the concentration

of titan

yellow

H.

A.

J.

PIETERS,

_-

W.

J.

HANSSEN,

VOL.

J. J. GEURTS

2 (1948)

I.400

1000

OIYOO

Fig. 3. The cxtmctlo~

cocficicnt
as a function
of the time, nftcr ncld~ng chffcrcnt qunntltics
of a mixture of stdrcti und glycerol
when the
Mg-content
is kept constant

Fig. 4. The cxtinctlon

cocfficicnt as a function of
the tlmc when dlffcrcnt qu.mtltics of gum arabic
;Lrc ~lclcd
11 = solutions contnmlng the same quantity of Mg
B = bt;lnk
Gum arnblc solution: IO g/l

i
I.0

a75

0.5

025

0.0

I
30

Ioc

OOOO

Fig. 5. The cxtinctlon

cocfficicnt as n function of
itlc titan yellow conccntriltlon
when tllc qunntlty
of Rig IS lccpt constant

Fig. 6. The extmction

coefficient
as a function
of the Mg-conccntratlon
when the quantity of
tltnn yellow is lccpt constant

15

4.3
-*mgk

VOL.

COLORIMETRIC

(1948)

DETERMINATION

OF

MAGNESIUM

245

Fig.6 gives the extinction as a function of the Mg content (titan yellow constant).
As long as the titan yellow is in excess, the extinction is a linear function of the
Mg content.
The required quantities of titan yellow arc expressed by the equation a > 2 x
+
2.4 (Table II).
Calcium deepens the colour of the solution. WC found that with IO mg Caf this
influence reaches a maximum value (Table III). In solutions containing IO mg Ca+a
the required quantity of titan yellow is:
I
TABLE
INPLUENCIS

ILL
OF

CALCIUX

Z5
0.326
0.336
0.348
0.35 I
0 350

IO

15
20
I

The lnflucncc
mum

Saturation

of Cil+a

Mognrsium hydroxide
sofuroted

0.645
0 780
0 828
0.832
0.830

hydroxrde
unsoturotsd

MOpQsiUm

rcnchcs

Fq.
7.
vnlucs in the prcscncc

maxI-

-mg

of Ca

a >
IO mg titan yellow

is sufficient

3 x + 3.5 (Fig.

for quantities

M9

7)

up to

mg Mg.

APPLICATIONS

I. Determinatiozzs

of Mg+2 in water .

Different quantities of a dilute solution containing

into IOO ml flasks, were mixed with
5

ml
ml
10 ml
x0.0 ml
10.0 ml
IO

and filled to the

determined.
References p. 253.

mark

s = o -

mg Mg+2, pipetted

calcium chloride (2 mg Ca+ per ml)

glycerol
starch solution (20 g/l)
titan yellow (I g/l)
sodium hydroxide (2.0 n)

with

distilled

water.

After

hour the extinction

was

I-I. A. J. PIEI-ERS, W. J. HANSSEN,

246

Table IV and Fig. S show us that the extinction

of the Mg-2 content (x) :
& =

0.500

x -=

EXTINCTION

- x

J. J. GEURTS

coefficient

VOL. 2 (1948)

(E) is a linear function

0.347

E - 0.347
0.500 -

TAI3LE
IV
CODFFICIF.N~ ~5 A I-UNCTION OF
l1lL3 QUANTI ry 01 nlAcir4Islunr

0 010

0 000

0.934

I ZOG

_x =

E -

0.34

0.500

F16.8. The cxtlnctton cocffhcnt. as il functron

of the qunntlty of hIf~$+~In pure soliillons

720

WC then determined
the influence of -41, Fe (II), Fe (III),
From Tables V, VI, VII and VIII, we set that the maximum
do not interfere arc:
0.05 mg Al
0.05 mg Ye
5
7g PO,
0.5 mg SiO,
per IOO ml of the dilute solution, containing

I80
-w

x = o-

47

POj3 and SiO,.

quantities which

mg Mg.

SiO, and scsquioxidcs are eliminated in the well-known

way. In the filtrate
from the iron- and aluminium hydrosides the Mg+2 is determined colorimctrically,
This filtrate contains relatively large amounts of alkali- and ammonium chlorides.
From Table IS and S we conclude, that sodium chloride diminishes the extinction
and increases the time of dcvclopmcnt of the colour to 2 hours. The NaCl also
Rcfcmces

p. 2.53.

VOL.

COLORIMETRIC

2 (x948)

TABLE
INFLUENCE

OF

DETERMINATION

OF MAGNESIUM

247

TABLE

ALUMINIUM

INI-LUENCE

OF

VI

FC

(XI)

AND

PC

(III)

Present mg
IbIg+

Al+3

0.500
O.4 73
o-297

0 05

0.300

0.1

o.G
,
>

0.2Q6

0
<o

0.1
0.2

0.5

0.05 mg A1+3 per x00 ml intcrfcrc

VII

INILUENCE

Prcscnt
BIb+10P0,-3
0

I .oz)

Ol-

PtIOSIiIATES

mg
--

&

mg rag+?
found

o-3.37

0.00

0.880

r.ng

0 .8 ; 3

mE:

pod3

0.240

0.170
I

0.05

o.G53

0.1

o&+0

0.2
05

OX,32

o.59G
0.570
0 554

0.615

0.520

._.___--1100 ml lnlcrfcrc
0.05 mg Fc per

TABLE

INI-I.UENCC

o 88G
o 89-1

OI-

\I11

DISSOLVED

slo,

0.8Q.1

0.83 I

1.1

1.10
1.1

I
II

0.5
0 Go8

per 100 ml leas no influcncc

0.608
0.582
0.554
0.508
0.48G

o.G78
o GG5

I---II
<

0.288

07

2
3
5

0.298

o Goo
TABLE

0.504
o.skQQ
0.4 75
O.*i,IO

0.05

0.300

3.12

00

1.5

2.0

TABLE
INFLUENCE

Or

>

IX

SODIUM

--0 5 mg SIO, per 100 ml lntcrfcrc

TABLE

CHLORIDE
INILUENCX
Ol-

OF

RCACTION

SODIUX
IS

X
CHLORIDE.

VARILD

FROM

TIIL
I

t.0

TIME
HOURS

Prcscnt mg
Rrgfa

0.790
0 790
0.776
0.782
0.779
o.77G
o.77G

60
80

100

I .03

120

140
IGO
180

I
I 400 mg NaCl per x00 ml mtcrfcrc
References p. 953.

NaCl glvcs a constant vnluc from 2 to 3 hours

after the ncldltlon of titan yellow and sodrumhyclroxldc

H.

248

A. J, PIETERS,

W.

J. HANSSEN,

J. J. GEURTS

VOL.

2 (x948)

influences the proportion x (Mg+z): a (titan yellow). With x < 1.8 mg of Mg+a
in the presence of I g NaCl we have to add 15 mg titan yellow. For this reason
the maximum quantity of Mg+2 which can be determined is 1.8 mg. Fortunately
the quantity of NaCl in the filtrate is always the same, as the quantity
of sodium
hydroxide
which is used to fuse the silicates is practically constant (We always
use 8 grams of NaOH per gram of the sample). Ammonium chloride interferes
when more than 2 mg is present. Therefore we have to eliminate it by evaporating
the filtrate and driving off the ammonium chloride by heating the residue.
TARLE

XI

TIIE EXTINCTION
COEPFICIENT
Ab A FUNCTION
OF
THE
QUANTITY
OP nlhCNE5IUnI
IN
THE
PRESENCE
OF soDIunr
CI-ILORIDE
AND
15 rng
INSTEAD
OIr IO mg TITAN
YELLOW
Prcscllt

rng

&

RI&a

NaCI

I .200
I .500

1.800

~TK:+~

found

0.325

0.300
o.Goo
0.900

1000

rng

0.510
0.680
0.850
I .032

0.310

1.212
I .qoz

l..w6
1.81~

o*5gg
0.886
I.192

1
WhCn

X =

m&

Of hfg+l

x=

E-

0.325
o.Goo

Fig. g. The cxtinclion cocfficicnt ;LSR function

of the quantity of Mg+a In the prcscncc of
I &ram
of sotlinm chloriclc

We determined the extinction

Mg+2 and I g of NaCl (Table XI,

coefficient of solutions containing

Fig. g) and found that:

0-1.8

mg of

E = 0.600 - x + 0.325
x

& -

0.325

0.600

We checked the method with synthetic silicates (Table X;I). The method saves
much time (Table XIII)
and is more accurate than the gravimetric
method
(Table XIV).
Rcfermces

p. 253.

VOL. 2

(1948)

COLORIMETRIC

DETERMINATION
TABLE

DETERMINATION

OF

Composition
SiO,
A202

OF MAGNESTUM

249

XII

MAGNESIUB!

IN

SYNTHETIC

SILICATES

of the silicates in o~ by weight

50.0
31.0

Fc202
cao

8
4

MgO
SO4

0.0-3.0
rest

Y0 nrgo
prcscnt

found

&

0.00
0.50

o-378
0.544
0.700
0.81 I
0.954
1.123
1.207

I .oo

1.50
2.00
2.50
3.00
hlonk (Inclucllng
L g N&l)

0.0

0.6
1.1

x.5
2.0
26
2.9

o-333

The error IS nboutlg%

TABLE
TIME

REQUIRED

A. in water

FOR

hrcthod

HOURS

Total
duration

Dctermmatlon

Worklng
hours

24
wltll the filtrate

32

IN

IIOURS

including

Photometric

Working
hours

Total
duration

of the sesquloxidcs)

Gravlmctrlc
Total
duration

TIME

References p. 253.

Photometric

Dctcrminntlon

Working
hours

B. In slllcntcs (starting
to drlvc off the NH,-salts.

IN

Gravimctrlc

Preparation : Elimination
of SiO,, Al, Fc and Cn

15

DETERIIINATION

.
TIME

Total
duration

XIII
THE

Working
hours

Total
duration

314

Workmg
hours
114
the time rcquircd

Il. A. J. PIETERS,

250

J. HANSSEN,

W.

TAI3LE
CO?dPARISON

OP

TlIR

RESULTS

sxnlrm

Prcwnt

0.00

0.50
1.00
1.50
2.00

2.50
3.00

Not corrcctccl

OF

TZIE

AND

VOL.

J. GEURTS

2 (1948)

XIV

DETERhlINATION

DI~ECIPITATION

J.

01

RI6

IN

SILICATES

l3Y

THE

CRAVIMETRIC

n7rmIoD

*I-J~E x~1IoTonlrxxIc

FOUtlCl

gcnv~mctr~cdlly
o 15-0

0.85-0.3

15 (blank)

1.4-1.5
I .85-l .9
2 3 -1.3
2.7 -2.&i
3.2 -3.2

error*

error

fotomctr~cxlly

-I_ 0.15
-I- C-J
1
-I- 0.45
-I- 0 4
-b 0.3
f 0.25
_1- 0 2

0.0

0.6
I

1.5

0.1
0.0

20
2.6
2.9

2:

+
-

:::
0.1

for tllc bhnk.

RECOMMENDED
a.

Delevmi?taLion

PROCEDURE

o/ Mgk2 in waler

I. Primiplc
When sodium hydroxide is added to a solution of Mg+2 which contains a suitable
protecting colloid and titan yellow in excess the magnesium hydroxide combined
with the dye gives a relatively rather deep coloured colloidal solution, the extinction coefficient of which is a linear function of the Mg content. The influence
of Ca+ is eliminated by adding Ca+2 in excess,
2.

Reagents
a.
b.
c.
d.
e.

Calcium chloride, 2 mg Ca-- per ml

Glycerol (C. P.)
Starch, 20 g/l
Titan yellow, I g/l
Sodium hydroxide, 2 N

3. Samfile
Start with V = maximal 50 ml of the sample, containing
of Mg+2.

not more than

mg

4. Pvocen?wc
Transfer V ml of the sample to a IOO ml measuring flask and dilute to 50 ml.
Add successively
5 ml calcium chloride
x0 ml glycerol
I0
ml starch solution
10.0 ml titan yellow solution and
10.0 ml sodium hydroside.
12cfcrc?tccs p. 253.

VOL.

2 (1945)

COLORIMETRIC

DETERhIINhTION

OF

BIAGNESIUfiI

Mix after each addition.

Fill to the mark with distlllcd water and mis. Determine
cient after I hour at different depths of layer.

the cstinction

251
coeffi-

5. Result
Calculate

the quantity

whcrl L = tllc cstinction

E, = the cstinctioI1

of RIg+z (s mg) present in 1 ml of the sample:

E---E
*x = _-_o
o-5
cocllicwnt of the solution
cocficicnt of a blank

6. Rmnnrk
a) The solutions of starch and titan yellow must be preparccl daily
b) 50 ml ol the sample must not contain more than

0.05
0.05
5.0
0.5
300

mg
mg
mg
mg
mg

Fe
Al
PO,
SiO,,
electrolytes

I. PrincipZc

An aliquoi portion of the filtrate from the hydroxides of Fe and Al, from which
the ammonium salts have been elimmatcd, is treated with titan yellow and sodium
hydroxide.
after the addition of a suitable protecting
colloid. The c.xtinction
cocfficicnt of the red solution is a linear function of the quantity
of Mg. The
influence of the reagents is determined by a blank.
2.

Sample

a. Silicates which can bc decomposed

quantitatively
by hydrochloric
acid.
Eliminate the SiO,, dilute the filtrate in a measuring flask to 250 ml, and take
IOO ml from which the iron and aluminium
are eliminated as the hydroxides by
double precipitation.
Collect the filtrates and fill up to 250 ml. Take a portion of
this filtrate, containing not more than 1.8 mg Mg, evaporate in a porcelain disk
and eliminate the ammonium salts by heating. Prolong the heating for 1.5 hours
at 550 C. Take up the residue in water and transfer to a IOO ml measuring flask.
Proceed as described in the procedure for water.
b. Silicates which have to be fused with sodium hydroxide or alkalicarbonates.
I g of the sample is fused in a nickel crucible with S g of NaOH or in a platinum
cruclblc with II g of N&O,.
The SiO, is eliminated in the well-known way. The
filtrate from the SiO, is transferred to a measuring flask and diluted to 250 ml.

H. A. J. PIDTERS,

252

W. J. HANSSEN,

J. J. CEURTS

VOL.

(1948)

In 200 ml of this filtrate the iron and aluminium are eliminated by double precipitation. The filtrate from the hydroxides is made up to 250 ml. Proceed with
V ml of this solution (set Table II).
y0 nigo cxpdd

p-7

0-8)
4-B

ldd
50
25
15

8-12

mg NnCl
500
750

Evaporate the V ml of the solution in a porcelain disk, drive off the ammonium
salts and heat 1.5 hours at 550 o C. Dissolve the residue in water and transfer to
a IOO ml measuring flask and dilute to 50 ml.
3. Reagents
a. Calcium chloride, 2 mg CaC2 per ml
b. Glycerol (C.P.)
c. Starch solution, 20 g/l
d. Titan yellow solution, 1.5 g/l
e Sodium hydroxide, 2.00 n
f. Sodium chloride, IOO g/l
4. Procedure
Add to the solution in the measuring flask successively:
5
ml calcium chloride
ml glycerol
IO
IO
ml starch solution
10.0 ml titan yellow
10.0 ml sodium hydroxide
Mix after each addition. Pill up to the mark and mix
coefficient at different depths of layer.

Determine

the extinction

5. Resaclls
Calculate the quantity

of MgO (x mg) present in V ml of filtrate:

(E, + p) - 1.658
0.600
coefficient of the solution
coefficient of the blank containing IO ml sodium chloride solution
between a blank, starting with the reagents used to eliminate the
the sesquioxides, and the E,

x=

& = extinction
E, = extinction
P = difference
SiO, and

E-

6. Remarks
The solutions of starch and of titan have to be prepared
Rcfcrcrrccs

p. 253.

daily.

VOL.

2 (1948)

COLORIMETRIC

DETERMINATION

MAGNESIUM

OF

253

SUMnIARY
From a critnxl study of the colorimctrrc tlctcrmmatron
of magnesium with titan yellow
WC concluded that:
a. titan yellow must bc present in cxccss;
b. a mixture of glycerol and starch solutron is satisfactory as protecting collo~d;
c. the influence of calcrum bccomcs constant with conccntratlons
IO mg Ca+? per IOO ml:
d. aluminium, iron, phosphate, ammonium and srhca mtcrfcrc;
e. alkali-ions interfck when prcscnt in large quantltlcs.
The method IS rapid and the accuracy is sntlsfactory
and can bc rccommcndcd
for the
dctcrmmation
of bfg+ in water and In silicates.

On n 6tud16 la d6tcrmmatron
photomctrlquc
du magn6slum ct dkrtt Its condltlons qul
donncnt dcs rkultats satisfaisants. Cc sont. ~diinc dc trtnnc cn cxces, melnngc clnmitlon ct dc
glyckrol pour stalxliscr lhydroxydc
du mngnksmm, prbcncc
dunc qunntit6 convcnablc dc
calcmm (lmflucncc du Ca +s attcint uric valcur maximum ct constantc).
Lalummlum,
lc fer, lc phosphate ct lammonium
nc pcuvcnt Ctre pr6sent.s quc dans dc
tr&s falblcs conccntratlons.
Lcs ions Na+l ct K+s nc donncnt dcs difhcult6s quA dcs concentrations 61~~6~s. La m6thodc
a bt& apphqu6c a lannlysc dcs caux et dcs slhcntcs. Ellc cut rnpulc ct plus cxnctc quc la methodc
gravimbtriquc.
ZUSAMMENFASSUNC
Die photomctrischc
Mngncslumbcstimmung
wurdc studlcrt
uncl die Bcdmgungcn
bcschricbk,
die hefrrcdigcnd~ Rcsultatc crgcbcn. Dlcsc sind :
Ubcrschuss Titaneclb.
Gcmisch von Amidon und Glvzcrol. urn tlas hIa~ncsiumhyclroxyd
zu stabilisicren, An&schhcrt
cmcr passcndcn Mcngc K&urn-(dcr
Elnfluss ion Cn+3-crrcicht
cm konstantcs Maximum).
Alumimum, Eiscn, Phosphat und Ammonia durfcn nur in schr schwachcr Konzcntration
vorhanden sein.
Na+ und K+ vcrursachcn nur Schwrcrigkcitcn bci stdrlccrcn Konzcntrntioncn.
Die Mcthodc
wurdc zur Wasscr- und Sihlcatanalysc angcwnndt. Sic 1st schncll und gcnaucr als dlc gravimctrrschc Bcstimmung.
REFERENCES
1 H. G;INSB&RG,
9 I;. SINIGAGLIA,
3 E.

C. LUDWIG,

EZcklroch..
Die Ckewzc.

2.

C. E.

4 Lab. dcr Atlas Wcrkc

45 (rg3g)
55 (1942)

JOHNSON,

A.G.,

Eng. C/r., Rnnl.

Ed.,
Chemte,
55 (1934) 218.

Imi.

Die

829.
36.).

r.+ (rgqz)

895.

6 C. URMHC.
R. BARIL, Mtltrochemxe,
14 (1934) 343.
e 13. LANGE,
KoCorrmelrtscire
AnaZyse,
gG (1941).
7 I;. D. SNELL, C. T. SNELL, Coloranrefric naethods of analysas,
47G (19.15).
s E. 13. SANDELL.
Coloramelric
dcfermrnaf~ons
of l~accs of wzfaLs. 305 (rg+.{).
0 Sfamiard
melhods fov fhs exama~~afzon of wafer ntld scwagre (IgqG)
p. Gr .
10 ZULKOWSKY,
Die Clrerrrie, 53 (1942) 218.

Received

February

zoth,

Ig48