Pure&Appl. Chem.,Vol. 61, No. 6, pp.

1133-1138, 1989,
Printed in Great Britain.
@ 1989 IUPAC

INTERNATIONAL UNION OF PURE

AND APPLIED CHEMISTRY
ANALYTICAL CHEMISTRY DIVISION
SUBCOMMITTEE ON ENVIRONMENTAL ANALYTICAL CHEMISTRY*?

DETERMINATION OF pH IN
HIGHLY SALINE WATERS
Prepared for publication by
Y. MARCUS
Department of Inorganic & Analytical Chemistry,
Hebrew University, Jerusalem 91904, Israel

*Membership of the Subcommittee during 1985-89 when the report was prepared was as follows:
Chairman: J. Buffle (Switzerland); Secretary: H. P. van Leeuwen (Netherlands; 1987-89);
Members: G. E. Batley (Australia; 1985-87); W. Davison (UK); R. A. Durst (USA); E.
Grushka (Israel; 1985-87); J. Jordan (USA); R. Kalvoda (Czechoslovakia); R. C. Kapoor
(India); D.Klockow (FRG; 1987-89); H. P. van Leeuwen (Netherlands; 1985-87); J. G.
Osteryoung (USA); E . Pungor (Hungary); S. Rube1 (Poland; 1985-87); W. F. Smyth (UK;
1985-87); J. Tarradellas (Switzerland; 1987-89); A. Zirino (USA; 1987-89).
+Title 1985-87: Subcommittee on Electroanalytical Methods of Environmental Trace Analysis
of the Commission on Electroanalytical Chemistry.

Republication of this report is permitted without the need for formal IUPAC permission on condition that an
acknowledgement, with full reference together with IUPAC copyright symbol (0 1989 IUPAC), is printed.
Publication of a translation into another language is subject to the additional condition of prior approval from the
relevant IUPAC National Adhering Organization.
 Determination of pH in highly saline waters

Abstract - The problem of t h e measurement of the o p e r a t i o n a l pH i n n a t u r a l

and a r t i f i c i a l highly s a l i n e waters ( s a l i n i t y g r e a t e r than i n ocean water)
i s discussed, and t e n t a t i v e recommendations by which reproducible and
meaningful r e s u l t s can be obtained a r e presented.

INTRODUCTION

A series of r e p o r t s from t h i s Commission has d e a l t with t h e measurement of t h e pH of

n a t u r a l waters: f r e s h waters ( r e f . l), sea water ( r e f . Z ) , and sea water and e s t u a r i n e
waters ( r e f . 3 ) . This r e p o r t r e p r e s e n t s t h e conclusion of t h e series, d e a l i n g with highly
s a l i n e waters, i . e . , waters having a s a l t content h i g h e r than t h a t of ocean water
0
( a s a l i n i t y of > 35 Such waters can be l a r g e n a t u r a l bodies of waters, such a s the
/oO).
Dead Sea o r t h e Great S a l t Lake, o r smaller ones, such as various lagoons and sabkhas i n
a r i d zones, where evaporation o f t e n exceeds renewal, hence causing high s a l i n i t i e s . How-
e v e r , t h e problem encompasses a l s o a r t i f i c i a l bodies of waters and i n d u s t r i a l b r i n e s , such
as s a l t pans, mining waste waters, e t c . The s p e c i f i c a t i o n of t h e waters d e a l t with i n t h i s
r e p o r t i s , t h u s , t h a t they contain a high concentration of n e u t r a l salts (mainly
c h l o r i d e s ) and n e g l i g i b l e concentrations of mineral a c i d s . Knowledge of t h e pH of such
waters i s of both academic i n t e r e s t i n t h e f i e l d s of geochemistry, marine chemistry and
biology, and hydrology, and of p r a c t i c a l importance f o r process chemistry, corrosion, and
waste management.

It i s a common p r a c t i c e t o measure t h e pH of n a t u r a l waters by means of an electrochemical

c e l l comprising a g l a s s e l e c t r o d e (GE) responsive t o hydrogen i o n s and a reference e l e c -
trode (RE) t h a t involves a l i q u i d j u n c t i o n . The emf of t h e c e l l with t h e test s o l u t i o n ,
E ( X ) , i s compared with t h e emf of t h e c e l l with t h e same e l e c t r o d e s but with a standard
buffer sol ut i on, E(S):

RE I junction solution I solution x or s I GE

j

The pH of t h e test s o l u t i o n i s given by

where pH(S) is t h e pH value assigned t o t h e standard b u f f e r employed, g = (_R/F) I n 18,

i s t h e gas c o n s t a n t , _F is t h e Faraday c o n s t a n t , and E is t h e l i q u i d j u n c t i o n p o t e n t i a l
a c r o s s t h e boundary marked by j i n cell (1). -j

APPLICATION T O HIGHLY SALINE WATERS

The problems a s s o c i a t e d with t h i s kind of measurement relate t o t h e s t a b i l i t y and repro-

d u c i b i l i t y of t h e l i q u i d j u n c t i o n , hence of t h e E . v a l u e s , and t o t h e proper value of
-J
pH(S) t o be assigned t o t h e standard b u f f e r used f o r t h e c a l i b r a t i o n . Several methods
have been proposed t o overcome t h e s e problems, when pH i s t o be measured i n r e l a t i v e l y
d i l u t e s a l t s o l u t i o n s , up t o and i n c l u d i n g ocean w a t e r s , but they may not be a p p l i c a b l e t o
more h i g h l y s a l i n e waters.

One way t o e l i m i n a t e t h e problem of t h e l i q u i d j u n c t i o n p o t e n t i a l i s t o dispense with the

l i q u i d j u n c t i o n i t s e l f , and have t h e r e f e r e n c e e l e c t r o d e immersed d i r e c t l y i n t h e solu-

1134
 Determination of pH in highly saline waters 1135

t i o n s X and S ( r e f . 4 ) . A n Ag,AgCl r e f e r e n c e e l e c t r o d e is g e n e r a l l y s p e c i f i e d f o r such

measurements, and eq. ( 2 ) is then replaced with

The problem o f t h e E v a l u e s i s thus transformed i n t o a problem of t h e a c t i v i t y c o e f f i -

c i e n t s of t h e c h l o r i d e i o n s , rcl,which, however, is taken c a r e of i n t h e value of p H ( S ) ' ,
t h e pH assigned t o t h e s t a n d a r d b u f f e r . This procedure seems t o work well f o r measure-
ments i n ocean waters, where t h e t o t a l v a r i a b i l i t y of t h e s a l i n i t y and c h l o r i n i t y ( i . e . ,
gel) i s minor, and an a r t i f i c i a l sea water s t a n d a r d b u f f e r t h a t c l o s e l y matches t h e test
ocean waters i s an a p p r o p r i a t e s o l u t i o n t o t h e problem ( r e f . 4).
There are f o u r drawbacks t o t h e a p p l i c a t i o n of t h i s s o l u t i o n t o t h e p r e s e n t problem,
p e r t a i n i n g t o very d i v e r s h i g h l y s a l i n e waters. One i s t h e a p p r e c i a b l e s o l u b i l i t y of
s i l v e r c h l o r i d e i n s o l u t i o n s t h a t are concentrated i n c h l o r i d e i o n s . This n e c e s s i t a t e s
t h e s a t u r a t i o n of t h e s o l u t i o n s with f r e s h l y p r e c i p i t a t e d s i l v e r c h l o r i d e f o r each
measurement ( r e f s . 5 , 6), s i n c e i n 3 mol/L aqueous sodium c h l o r i d e ( 3 . 2 molal) the
s o l u b i l i t y of A g C l i s about 0.003 molal (mainly a s AgC143-, r e f . 5 ) , and is s t i l l high-
er i n , s a y , waters of t h e Great S a l t Lake (about 4.9 molal i n c h l o r i d e ) or t h e Dead Sea
(about 7.2 m o l a l ) . Another drawback is t h e danger of t h e poisoning of t h e Ag,AgCl
r e f e r e n c e e l e c t r o d e with bromide o r s u l f i d e i o n s t h a t may be p r e s e n t i n t h e s e s a l i n e
waters. (The Dead Sea is about 0.07 molal i n bromide.) Y e t another drawback i s t h e l a r g e
range of s a l i n i t i e s and c h l o r i n i t i e s encountered i n t h e waters t h a t are t h e s u b j e c t of t h e
p r e s e n t r e p o r t . A wide range of standard b u f f e r s would have t o be prepared and assigned
pH(S) v a l u e s , i n o r d e r t o match t h e test s o l u t i o n s a t a l l c l o s e l y . This is e v i d e n t l y
i m p r a c t i c a l . A f i n a l drawback i s t h e r e l u c t a n c e of workers i n t h e f i e l d t o use anything
but t h e c o n f i g u r a t i o n noted i n c e l l (1) f o r p r a c t i c a l pH measurements, i n c o n t r a s t with
what l a b o r a t o r y r e s e a r c h e r s may be ready t o i n v e s t t h e i r time and e f f o r t s i n .

Since i t seems t o be necessary t o work with c e l l (l), i . e . , with a c e l l t h a t employs a

l i q u i d j u n c t i o n , e f f o r t s t o minimize t h e problems involved i n i t s use are r e q u i r e d . The
r e p r o d u c i b i l i t y o f t h e l i q u i d j u n c t i o n p o t e n t i a l s , E j , can be improved by a proper design
of t h e j u n c t i o n , and a J-type j u n c t i o n appears t o be t h e b e s t . The j u n c t i o n between the
j u n c t i o n s o l u t i o n and t h e s o l u t i o n X o r S i s formed i n t h e v e r t i c a l c a p i l l a r y t h a t i s t h e
s h o r t l e g of t h e J - t u b e , with t h e j u n c t i o n s o l u t i o n below. A renewable j u n c t i o n can be
formed i f t h e j u n c t i o n s o l u t i o n can be pushed o u t from t h e J-tube by t h e reference
e l e c t r o d e assembly placed i n i t s long l e g ( r e f . 7 ) . This renewal a l s o guards t h e inner
r e f e r e n c e e l e c t r o d e from contamination by components of t h e test s o l u t i o n . A constant
geometry a t t h e j u n c t i o n and a c o n s t a n t composition of t h e j u n c t i o n s o l u t i o n a r e assured
i n t h i s manner, hence reproducible values of E. should be obtained.
-J
The p r e c i s i o n of t h e pH measurements being provided f o r by t h e proper design of t h e l i q u i d
j u n c t i o n , t h e i r accuracy can, i n p r i n c i p l e , be improved by a reduction of t h e absolute
values of E . ( S ) and E ( X ) . For t h e common j u n c t i o n s o l u t i o n employed, 3 . 5 mol/L potassium
-J -j
c h l o r i d e , used i n combination with t h e calomel r e f e r e n c e e l e c t r o d e , t h e value of E . ( X )
-J
with r e s p e c t t o t h e highly s a l i n e test s o l u t i o n s X should be very s m a l l , b u t i t i s l a r g e
with r e s p e c t t o t h e d i l u t e s t a n d a r d b u f f e r s o l u t i o n s S (NBS b u f f e r s ) recommended by IUPAC
f o r g e n e r a l use i n aqueous s o l u t i o n s having i o n i c s t r e n g t h s < 0 . 1 molal ( r e f . 8 ) . For a
calomel e l e c t r o d e i n s a t u r a t e d KC1 t h e l i q u i d j u n c t i o n p o t e n t i a l with r e s p e c t t o d i l u t e
aqueous b u f f e r s o l u t i o n s i s E = 3 . 2 mV ( r e f . 9). The s u c c e s s f u l employment of t h e d i l u t e
-3
standard b u f f e r s depends on t h e f a c t t h a t although both E j (S) and E . ( X ) are non-negligible
-J
under t h e s e such c o n d i t i o n s , t h e s e q u a n t i t i e s are c o n s t a n t and p r a c t i c a l l y e q u a l , hence
cancel o u t . A s mentioned above, t h e E . values are n o t equal when X is a highly s a l i n e
-J
water and S i s a d i l u t e s t a n d a r d b u f f e r . Then although c o n s t a n t E . ( S ) and ( n e g l i g i b l e )
-J
Ej(X) can be achieved, they w i l l n o t cancel o u t . Nor can E j ( S ) be c a l c u l a t e d t o a
s a t i s f a c t o r y accuracy, even with a w e l l defined geometry of t h e l i q u i d j u n c t i o n , because
of l a c k of adequate knowledge of t h e a c t i v i t y c o e f f i c i e n t s i n t h e mixed e l e c t r o l y t e solu-
t i o n s involved.
1136 SUBCOMMllTEE ON ENVIRONMENTAL ANALYTICAL CHEMISTRY

It i s expedient t o rewrite eq. ( 2 ) i n t h e following manner:

The f i r s t term on t h e r i g h t hand s i d e of eq. ( 4 ) i s a c o n s t a n t , i f t h e d i l u t e NBS b u f f e r s

a r e employed, b u t i s unknown, whereas t h e l a s t term is probably n e g l i g i b l y small, provid-
ed highly s a l i n e test s o l u t i o n s X are used. Therefore, t h e d i f f e r e n c e i n pH between two
such test s o l u t i o n s can be measured i n such a c e l l :

assuming E.(X1) - E ( X ) t o be e f f e c t i v e l y z e r o . That t h i s i s , indeed, t h e case can be

-J j 2
concluded from s t u d i e s t h a t compared pH values measured i n c e l l s of type (1) with € Io
values ( H a m m e t a c i d i t y f u n c t i o n v a l u e s ) obtained by i n d i c a t o r s , i . e . , without involvement
of l i q u i d j u n c t i o n s ( r e f s . 10, 11).

For example ( r e f . l l ) , a d i f f e r e n c e of 0.03 u n i t s between pH and Ho i n 7 mol/L lithium

chloride containing < 1%hydrochloric a c i d corresponds t o IE. -J
1
( X ) of 1.8 mV between t h e
calomel/conc. K C 1 r e f e r e n c e e l e c t r o d e and t h e test s o l u t i o n . Another test s o l u t i o n of
s i m i l a r s a l t content b u t d i f f e r e n t pH would have p r a c t i c a l l y t h e same low value of E j , and
t h e premise f o r eq. ( 5 ) is v a l i d a t e d .

The e f f e c t s of t h e presence of high concentrations of n e u t r a l salts i n some n a t u r a l bodies

of water on t h e i r a c i d i t y a t a given concentration of hydrogen i o n s is of i n t e r e s t . The
phenomenon of i n c r e a s i n g pH values measured on Dea Sea waters on progressive d i l u t i o n with
d i s t i l l e d water beyond t h e i n c r e a s e expected from t h e lower hydrogen i o n concentration
i t s e l f has been noted ( r e f s . 12-14). This seems t o be a r e a l e f f e c t and not an a r t i f a c t of
t h e use of c e l l s of type (1) f o r t h e measurements. It was explained by Krumgalz ( r e f . 15)
i n terms of t h e s a l t e f f e c t on t h e a c t i v i t y c o e f f i c i e n t of d i v a l e n t anions p r e s e n t i n the
waters, s p e c i f i c a l l y carbonate. On t h e b a s i s of t h e a s s o c i a t i o n equilibrium c o n s t a n t s of
- 2-
hydrogen i o n s with HCO and C03 , K1 and ,&I the relationship
3

was obtained. This s i m p l i f i e s t o

PH = -log([H+l&) = - (1/2)log(K1K2) + (1/2)10g r(C032-) (7)

2
i f [HC03-]r* >> El, as is t h e case with sea water ()' i s t h e mean a c t i v i t y c o e f f i c i e n t
of H+ and HCO - ) . The extremely l a r g e decrease of t h e a c t i v i t y c o e f f i c i e n t of t h e d i -
3
v a l e n t carbonate anion with i n c r e a s i n g s a l t concentrations is thus mainly responsible f o r
t h e decrease of t h e pH from around 8.1 i n Mediterranean waters t o 6 . 0 i n t h e depth of the
Dead Sea. Again, t h a t t h i s is not an a r t i f a c t due t o t h e use of a reference electrode
with a l i q u i d j u n c t i o n was demonstrated by Ben-Yaakov and Sass ( r e f . 16) u s i n g measure-
ments i n a c e l l with an AgC1,Ag e l e c t r o d e without a l i q u i d j u n c t i o n on a r t i f i c i a l Dead Sea
water.

It h a s been argued by Bates and Dickson ( r e f s . 2 , 17), among o t h e r s , t h a t a primary a p p l i -

c a t i o n of pH measurements i n s a l i n e media such as sea waters i s t h e determination of the
acid/base s p e c i a t i o n of a conjugate acid/base system:

[acid]/[base] = (l/Ka) [H'] (8)

where t h e square b r a c k e t s may denote mol/L, mol/(kg water), or mol/(kg s o l u t i o n ) and the
a c i d d i s s o c i a t i o n q u o t i e n t , Ka, i s i n t h e a p p r o p r i a t e u n i t s . I f t h e thermodynamic acid
0
d i s s o c i a t i o n equilibrium c o n s t a n t , Ka , i s used i n eq. (8),i t s r i g h t hand s i d e must be
m u l t i p l i e d by (YbaseYH/yacid) f o r t h e mol/L s c a l e and with t h e a p p r o p r i a t e o t h e r a c t i v i t y
coefficient quotient f o r the other scales. I n ocean water of c o n s t a n t s a l i n i t y ( s a y ,
350/00) t h e r a t i o (ybase/zacid) i s approximately c o n s t a n t , and may be incorporated with Ka
into a E a t , and t h e product EIH = [H'] YH can be defined a s 10-PH. However, Ka w i l l , in
g e n e r a l , depend on t h e s a l i n i t y , and a value determined f o r ocean water (of s a l i n i t y
0
35 /oo) would n o t be a p p l i c a b l e i n d i v e r s highly s a l i n e waters. Thus, t h e d e f i n i t i o n
pH = -log + = - l o g [H+] yH w i l l n o t be g e n e r a l l y u s e f u l . Its o p e r a t i o n a l d e f i n i t i o n i n
 Determination of pH in highly saline waters 1137

terms of c e l l (1) and eq. ( 5 ) , with t h e s o l u t i o n X2 i d e n t i f i e d with a s u i t a b l e standard

b u f f e r , is t o be p r e f e r r e d , as i s i n f a c t , t h e accepted p r a c t i c e .

It is s t i l l necessary t o choose among t h e o p e r a t i o n a l d e f i n i t i o n s of pH and t h e r e l a t e d

s t a n d a r d i z i n g b u f f e r s t h e one most a p p r o p r i a t e f o r d i v e r s h i g h l y s a l i n e waters. The pH
s c a l e s t h a t have been used (see r e f s . 2 , 4 , 17) f o r ocean waters i n c l u d e t h e following.
- pHNBS, u s i n g d i l u t e aqueous b u f f e r s f o r s t a n d a r d i z a t i o n .

- pHt, t a k i n g i n t o account sulfate-bound hydrogen i o n s .

- pmH, using tris i n s y n t h e t i c sea water f o r s t a n d a r d i z a t i o n .

When s t a n d a r d i z a t i o n is c a r r i e d out with t h e d i l u t e aqueous b u f f e r s (NBS b u f f e r s ) , the

r e s u l t i n g pHNBS has t h e disadvantage of including t h e r e s i d u a l l i q u i d j u n c t i o n p o t e n t i a l
( s e e above), so t h a t i t corresponds t o n e i t h e r - l o g [H'] nor - l o g +
a (on any of t h e con-
centration scales). This problem should be aggravated f o r waters t h a t are t h e s u b j e c t of
t h e p r e s e n t r e p o r t , i . e . , more highly s a l i n e than ocean water, s i n c e t h e r e s i d u a l l i q u i d
j u n c t i o n p o t e n t i a l would be l a r g e r .

-
The ' t o t a l ' hydrogen i o n concentration, 'free' and bound t o s u l f a t e i o n s a s HS04 , has
been proposed by Hansson as t h e q u a n t i t y t o be described by t h e pH measurement i n ocean
water ( r e f . 4 ) . This is because ocean water contains an a p p r e c i a b l e concentration of
s u l f a t e , about 0.03 mol kg
-1
. With s u b s c r i p t t d e s i g n a t i n g t o t a l , t h e following r e l a t i o n -
s h i p w i l l be obeyed:

pHt = -log[H+] - l o g (1 + [SO4

2-
]/Ka(HS04-))

where Ka(HS04-) i s about 0.08 kg mol-l. However, i n d i v e r s h i g h l y s a l i n e waters the

s u l f a t e c o n c e n t r a t i o n may be n i l or any value, and such waters may c o n t a i n o t h e r bases,
beside s u l f a t e , t h a t bind hydrogen i o n s ( f l u o r i d e , phosphate, carbonate, s u l f i d e , b o r a t e ,
e t c . ) . Furthermore, t h e r e s p e c t i v e Ea values w i l l depend on t h e composition and i o n i c
s t r e n g t h of t h e p a r t i c u l a r s a l i n e water s t u d i e d . I n such waters, t h e r e f o r e , t h i s concept
of ' t o t a l ' hydrogen i o n concentration has l o s t t h e a t t r a c t i v e n e s s i t may have f o r ocean
waters.

On t h e o t h e r hand, s t a n d a r d i z a t i o n with a standard tris b u f f e r ( t r i s (hydroxymethyl)

methanamine) i n s y n t h e t i c sea water ( r e f . 4 ) does have i t s merits with r e s p e c t t o the
p r e s e n t problem. I n a sulfate-containing (0.0293 molal) s y n t h e t i c sea water of 350/oo
s a l i n i t y a t 25'C, t h e 0.04 molal equimolar tris b u f f e r has a pHt ( - l o g m H t ) of 8.201
according t o Ramette e t a l . ( r e f . 18). I n a s u l f a t e - f r e e s y n t h e t i c s e a water of t h e same
s a l i n i t y t h i s would correspond t o 8.331, accfrding t o eq. ( 9 ) (see a l s o r e f . 2 ) . Values
a t some o t h e r temperatures between 5 and 40 C were a l s o published. The p r e c i s i o n of the
measurements was very h i g h , mean d i f f e r e n c e s between d u p l i c a t e s being 0.05 mV, correspond-
i n g t o 0.0008 u n i t s i n pH ( r e f . 18). The value of pH(S) assigned t o t h e equimolar 0.04
molal tris b u f f e r i n s u l f a t e - f r e e s y n t h e t i c s e a water should t h e r e f o r e be r e l i a b l e t o
b e t t e r than 50.003 units.

Dickson ( r e f . 17) s t a t e d t h a t t h e use of ( s t a n d a r d ) b u f f e r s based on a s e a water back-

ground, having n o t y e t found any following w i t h i n t h e oceanographic community, would be
i m p r a c t i c a l i n a regime where i t is impossible t o match t h e background composition of the
b u f f e r with t h a t of t h e sample ( e . g . , b r i n e s ) , Nevertheless, t h e c o n s i d e r a t i o n s propound-
ed by Khoo e t a l . ( r e f . 19) make i t seem l i k e l y t h a t s t a n d a r d s prepared i n s u l f a t e - f r e e
s y n t h e t i c (sea water) media o f f e r a s u c c e s s f u l means of s e t t i n g up a u s e f u l experimental
s c a l e f o r t h e determination of pH = -log mH i n s a l i n e waters.

I f t h e pH of a c i d i c or a c i d i f i e d b r i n e s is t o be determined, i t may be advantageous t o

s t a n d a r d i z e with a s o l u t i o n of a n e u t r a l b r i n e of similar composition t o t h e test s o l u t i o n
made, s a y , 0.01 m i n hydrochloric a c i d , provided t h i s s t a n d a r d i z a t i o n b r i n e does not
c o n t a i n conjugate bases of weak a c i d s . I n ignorance of t h e a c t i v i t y c o e f f i c i e n t of the
hydrochloric a c i d i n t h i s s t a n d a r i z a t i o n s o l u t i o n , no pH value can be assigned t o i t , but
n e v e r t h e l e s s i t has t h e c l e a r l y defined pgH value of 2.00.
1138 SUBCOMMITTEE ON ENVIRONMENTAL ANALYTICAL CHEMISTRY

RECOMMENDATIONS

I n view of t h e above d i s c u s s i o n , i t would be advantageous i f agreement could be reached

among t h e workers i n t h e f i e l d about t h e following p o i n t s .

1. The pH of h i g h l y s a l i n e waters should be measured with a c e l l of type (l), i . e . , with

a g l a s s e l e c t r o d e responsive t o hydrogen i o n s and a r e f e r e n c e e l e c t r o d e (such as calomel)
i n c o r p o r a t i n g a s a l t b r i d g e (3.5 mol/L KC1) t h a t provides a l i q u i d j u n c t i o n .

2. The design of t h e l i q u i d j u n c t i o n should be s o as t o a s s u r e m a x i m a l r e p r o d u c i b i l i t i e s

of t h e measurements, e . g . , with a J-type c a p i l l a r y and p r o v i s i o n s f o r renewing t h e junc-
tion.

3. The c e l l should be c a l i b r a t e d with an 0.04 molal equimolar tris b u f f e r i n s u l f a t e - f r e e

s y n t h e t i c sea water o f s a l i n i t y 350 /00 (according t o Khoo e t a l . , r e f . 19). This a r b i -
t r a r y choice is suggested i n o r d e r t o provide f o r uniformity of p r a c t i c e .

4. The r e s u l t s of t h e measurements should be on t h e pH = -log gH s c a l e , for ’free‘

hydrogen i o n m o l a l i t i e s , as t h i s i s t h e least ambiguous q u a n t i t y . The mol/(kg s o l u t i o n )
s c a l e may, however, be used i n s t e a d of t h e mol/(kg water) = m o l a l i t y s c a l e , i f t h i s i s
c l e a r l y s t a t e d and j u s t i f i e d .

5. Experimental work should be done t o confirm t h e assigned values of t h e pH of t h e

standard tris b u f f e r i n t h e s a l i n e medium s p e c i f i e d above over a wide temperature range.
I t should a l s o be demonstrated experimentally t h a t r e s i d u a l l i q u i d j u n c t i o n p o t e n t i a l s a r e
indeed minimized by t h i s choice of medium f o r t h e standard b u f f e r with r e s p e c t t o any
highly s a l i n e test s o l u t i o n .

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