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Potentiometric Determination
of Potassium in Seawater and
Interstitial Water
a a
G. Marquis & J. Lebel
a
Département d'océanographie , Université du
Québec à Rimouski Rimouski , Québec, Canada , G5L
3A1
Published online: 06 Dec 2006.

To cite this article: G. Marquis & J. Lebel (1981) Potentiometric Determination of

Potassium in Seawater and Interstitial Water, Analytical Letters, 14:12, 913-920, DOI:
10.1080/00032718108055489

To link to this article: http://dx.doi.org/10.1080/00032718108055489

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 ANALYTICAL LETTERS, 14(A12), 913-920 (1981)

POTENTIOMETRIC DETERMINATION OF POTASSIUM

IN SEAWATER AND INTERSTITIAL WATER

KEY WORDS: potassium, seawater, interstitial water

Downloaded by [York University Libraries] at 21:38 28 December 2014

G. Marquis 6 J. Lebel

Dgpartement d'oc5anographie
Universit6 du Qu6bec 2 Rimouski
Rimouski, Qugbec, Canada, G5L 3A1

ABSTRACT
A method i s described for the determination of potassium in

seawater and marine sediment porewater. After precipitation of

the halogen ions with AgN03, potassium is precipitated with sodium

tetraphenylborate. The excess tetraphenylborate is then deter-

mined by AgN03 titration, using a silver electrode for end-point
detection. Application of this method to seawater samples as
small as 1 cm3, gave accuracy and precision of better than 1%.

INTRODUCTION
1
Siska and Pungor showed that potassium in aqueous
solution may be determined by measuring the tetraphenylborate ion

913

Copyright 0 1981 by Marcel Dekker, Inc.

 914 MARQUIS AND LEBEL

(TPB) remaining in solution after the precipitation and separation

of potassium tetraphenylborate (KTPB). AgN03 is used as titrant

and the end-point is obtained potentiometrically. The sample must

be free of anions which form insoluble silver salts.

The silver nitrate titration used to determine the chlorinity

of seawater produces, at the completion of the analysis, a solu-

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tion which satisfies this condition since, at this point, all the

halides have been precipitated as silver salts. We have therefore

adapted the method of Siska and Pungor to seawater by first

removing the interfering halide ions through the chlorinity

determination, then precipitating dissolved potassium as the

tetraphenylborate salt, and finally measuring the excess tetraphe-

nylborate potentiometrically.

This method is equally precise as the classical gravimetric

method, which consists precipitating, recovering and weighing

2
potassium tetraphenylborate (Culkin and Cox ) , and has the

advantage that it can be carried out on a one milliliter sample.

METHOD
The analysis for potassium is based on the precipitation of

KTPB, whose solubility i n water is only 54 mgL-l, and the possi-

bility of back-titrating the TPB ions with silver nitrate.

Because of the necessity of working in the absence of chloride

ions, these must first be precipitated with AgN03 following the

3
procedure of Hermann . A 1 cm3 sample, weighed with a preci-
 POTASSIUM IN SEAWATER 915

sion of 2 0 . 1 mg, is placed in a 10 cm3 titration vessel and about

99% of the chloride ions are precipitated by adding a predeter-

mined amount of a concentrated AgN03 solution. The remaining

fraction is precipitated by potentiometric titration with a dilute

AgN03 solution, using a pair of indicating electrodes connected to

an automatic titrator to detect the end-point. When the end-point

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is reached, the solution is free of chloride ions, hence it is

important to determine the end-point with precision. Also, the

amount of dilute AgN03 added during the titration should be kept

at a minimum. It should not exceed 1cm3 in order to avoid too

much dilution and problems with the precipitation of potassium.

It is therefore useful to know the approximate chlorinity of the

sample.

In a second step the electrodes are rinsed with 1 cm3 of

distilled water, collected in the titration vessel. The potassium

is then precipitated by adding 2 cm3 of NaTPB solution (9.568 gkg-l)

and 1 cm3 of acetate buffer at pH = 5. The mixture is cooled a

few minutes in an ice bath to avoid degradation of the reactant

2 and vigorous agitation is then maintained for a period of 10

minutes. The precipitate is separated on a Buchner type filter

funnel with a fritted glass filter of porosity F. The titration

vessel and the filter are each rinsed with 1 cm3 distilled water.
The filtrate is transferred t o a 10 cm3 titration vessel for

potentiometric titration of excess TPB ions with dilute AgN03.

 916 MARQUIS AND LEBEL

The c o n t e n t of K i n t h e sample i s o b t a i n e d from t h e d i f f e r e n c e

between t h e amount o f TBP measured and t h e amount i n i t i a l l y added

Reagents

A l l r e a g e n t s used were "Baker Analysed Reagents". A sample

o f s t a n d a r d seawater o f c h l o r i n i t y 19.3770%, served t o s t a n d a r d i z e

t h e AgN03 s o l u t i o n . The following r e a g e n t s were p r e p a r e d :

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Ag+ - Concentrated AgN03 s o l u t i o n , about 46 g k g - l ,

s t a n d a r d i z e d by determining t h e c h l o r i d e c o n t e n t
3
i n s t a n d a r d seawater .
- D i l u t e AgN03 s o l u t i o n : 95.1928 g o f concentrated

solution per 1 L solution.

NaTPB Sodium t e t r a p h e n y l b o r a t e , about 10 g k g - l , standar-

d i z e d with d i l u t e AgN03.

Acetate b u f f e r 14.8 mL CH3COOH 0 . 2 M + 35.2 mL CH3COONa 0 . 2 M,

a t pH = 5 d i l u t e d t o 100 mL.

K+ K ~ S O L , , about 1 g kg-I

Apparatus

The measurements were c a r r i e d out with a Radiometer t i t r a t i o n

system c o n s i s t i n g of an automatic t i t r a t o r (TTT 6 0 ) , a 2.5 mL elec-

t r i c a l a u t o b u r e t t e (ABU 13) and a pH meter (PHM 64) w i t h k O . 1 mV

 POTASSIUM I N SFAWATER 917

p r e c i s i o n connected t o a recorder (REA 160/REC 6 1 ) . The t i t r a t i o n

was monitored with a s i l v e r e l e c t r o d e (P 4040) coupled with a

reference e l e c t r o d e wich c o n s i s t s of a s i l v e r wire sealed i n t h e

o u t l e t from t h e b u r e t t e containing t h e d i l u t e s i l v e r n i t r a t e s o l u -
5
t i o n , a s described by Hermann and Culkin

Results
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In order t o t e s t t h e r e p r o d u c i b i l i t y of t h e method a s e r i e s

of r e p l i c a t e measurements of potassium was made on a sample of

standard seawater of 35%0 s a l i n i t y . Table I shows t h a t t h e r e s u l t s

obtained, giving a K/C1 r a t i o of 0.0206, agree with Culkin and Cox

The standard d e v i a t i o n f o r t h e t e n r e p l i c a t e s i s 21.0%. The

same r e p r o d u c i b i l i t y was obtained on a sample of i n t e r s t i t i a l

water of c h l o r i n i t y - 22.5%o (Table 11).

In order t o a c e r t a i n t h a t t h e p r e c i p i t a t i o n of potassium i s

complete i . e . t h a t t h e amount of TPB ions t i t r a t e d does indeed

c o n s t i t u t e t h e excess and t h a t t h e r e i s no i n t e r f e r e n c e bv o t h e r

ions, d i f f e r e n t known amounts of K2S04 were added t o 1 cm3 standard

seawater of known potassium content. The r e s u l t s i n Table I11

show t h a t t h e amount of K recovered v a r i e s from 98 t o 102%. This

confirms t h a t t h e recovery i s quant t a t i v e and t h a t t h e r e i s no

systematic v a r i a t i o n r e l a t e d t o t h e amount of potassium added.

CONCLUSION

The determination of potassium by potentiometric back-

t i t r a t i o n of excess TPB ions c o n s t i t u t e s an accurate and r e l a t i v e l y

 9 18 MARQUIS AM, LEBEL

TABLE 1

R e p l i c a t e d e t e r m i n a t i o n s o f potassium i n a s e a w a t e r sample.
([Strong AgNO31 = 46.086 k g - l ; [ d i l u t e AgN031 95.1928 g
o f s t r o n g AgNO3 L-'; [NaTPB, = 9 . 5 6 8 g k g - l )

Sample NaTPB Volume o f CK'I K/C1

weight added d i l u t e AgNO,
(8) (g) (cm 1 (mg b - 1 ) (mg/%o,)
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1.0032 1.9892 1.753 403 0.0208

1.0016 2.0125 1.783 399 0.0206

1.0102 2.0033 1.771 39 8 0.0205

1.0074 1.9941 1.758 40 2 0.0208

1.0039 1.9924 1.764 396 0.0204

1.0065 2.0119 1.787 39 2 0.0202

1.0072 1.9894 1.750 405 0.0209

1.0157 1,9826 1.747 39 7 0.0205

1.0117 1.9886 1.753 399 0.0206

1.0027 1,9912 1.755 403 0.0208

Mean potassium c o n c e n t r a t i o n = ,399 mg k g - l ; s t a n d a r d d e v i a t i o n =

3 . 8 mg kg-I (1.0%)

1
simple method. The method d e s c r i b e d by S i s k a and Pungor

r e q u i r e s a sample s i z e o f 10 cm3, and t h e c l a s s i c a l g r a v i m e t r i c

2 4
method (Sporek ) as modified by Culkin and Cox needs 40 cm3.

Our t e c h n i q u e i s t h e r e f o r e o f p a r t i c u l a r i n t e r e s t f o r i n t e r s t i t i a l

water a n a l y s i s s i n c e i t o n l y r e q u i r e s a small sample and g i v e s

s i m u l t a n e o u s l y a p r e c i s e measurement o f t h e c h l o r i n i t y .
 TABLE I1

R e p l i c a t e d e t e r m i n a t i o n s o f potassium i n two i n t e r s t i t i a l water samples

([Strong AgN033 = 46,086 k g - l ; [ d i l u t e AgN031 = 95,1298 g
of s t r o n g AgN03 L-'; [NaTPBl = 9,568 g k g - I ) .

Station Depth Sample NaTPB Volume of CK l K/C1

weight added d i l u t e AgN03
# (cm) (g) (9) (cm3) (mg kg-') (mg/%oo)
~

22 CG 28-33 1.0275 2.0110 1.668 500 0.0223

1.0300 1.9961 1.660 491 0.0219

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1.0311 1.9940 1.653 495 0.0220

Mean potassium c o n c e n t r a t i o n = 495 mg k g - l ; s t a n d a r d d e v i a t i o n =

3 . 7 mg kg-l (0.8%)

2 2 CG 35-40 1.0258 1.9956 1.684 469 0.209

1.0303 1.9916 1.688 459 0.204

1.0274 1.9912 1.678 469 0.209

Mean potassium c o n c e n t r a t i o n = 466 mg k g - l ; s t a n d a r d d e v i a t i o n =

4 . 8 mg kg-l (1.1%)

TABLE I11

Recovery o f potassium added t o 1 m l seawater samples.

(CK'] added = 0.9979 g Kg-l)

K+ K+ K+ Kf K+
sample added total titr a t e d recovery
Cml) (mg) (mg 1 (mg) (%I

0.405 0.217 0.622 0.614 99

0.406 0.217 0.622 0.612 98

0.400 0.177 0.577 0.573 99

0.406 0.177 0.583 0.593 102

0.404 0.130 0.534 0.538 101

0.405 0.128 0.533 0.525 98

 920 MARQUIS AND LEBEL

However, one can only obtain a good precision by assuring a

complete precipitation of potassium. This is the most delicate

pzrt of the procedure, as is the case for gravimetric methods in

general. Nevertheless, a back-titration of an excess reagent

seems easier to carry out than isolating and weighing a prGcipitate,

and the results obtained are equally precise and accurate.

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ACKNOWLEDGEMENTS
The authors express their sincere gratitude to Dr. B. Sundby

for critically reading the manuscript. The financial support

necessary to carry out this work was assumed by the National

Sciences and Engineering Research Council of Canada and by the

Direction Gbnbrale de 1'Enseignement Sup6rieur du Qudbec.

REFERENCES
1. Siska, E. and Pungor, E. 1971. Potentiometric determination
of tetraphenylborate ions with silver nitrate. Determination
of silver, potassium and thallium (I). Z. Anal. Chem., 257 :
12-18.
2. Culkin, F. and Cox, R.A. 1966. Sodium, potassium, magnesium,
calcium and strontium in sea water. Deep-sea Research, 13 :
789-804.
3. Hermann, F . 1951. High accuracy potentiometric determination
of the chlorinity of sea water. J. Cons. Perma. Int. Explor.
Mer, 17 : 223-230.
4. Sporek, K.F. 1956. The gravimetric determination o f
potassium in sea water as the potassium - tetraphenylboron
salt. Analyst, 81 : 540-543.
5. Hermann, F.E. and Culkin, F. 1978. The preparation and
chlorinity calibration of standard seawater. Deep-sea
Research, 25 : 1265-1270.

Received &ril 22, 1981

Accqted June 1, 1981