The Preparation and Thermodynamic Properties of a Palladium-Hydrogen Electrode

M. J. Vasile and C. G. Enke

Frick Chemical Laboratory, Princeton University, Princeton, New Jersey

ABSTRACT T h e potential of a p a l l a d i u m - h y d r o g e n electrode p r e p a r e d by electrolytic methods was studied as a function of t h e composition of the electrode, t e m p e r a t u r e , and pit. T h e o b j e c t i v e of these studies w a s to p r e p a r e a p a l l a d i u m h y d r o g e n r e f e r e n c e electrode w h i ch can be used in h y d r o g e n f r e e solutions. T h e potential was found to be a function of the electrode composition in the a phase, and ~ phase, and i n d e p e n d e n t of composition in t h e a ~- ~ phase region. Equations w e r e d e r i v e d starting f r o m f u n d a m e n t a l t h e r m o d y n a m i c s w h i c h fit th e potential vs. composition data in t h e a phase, and in the a -~ phase region, as well as the t e m p e r a t u r e dependence for such an electrode. T h e p r o c e d u r e for p r e p a r i n g a p a l l a d i u m h y d r o g e n r e f e r e n c e electrode by e l e c t r o lytic methods is given. The absorption of gaseous h y d r o g e n f r o m aqueous solutions by p a l l a d i u m and the subsequent potential of the P d - H / H 2 system has been studied e x t e n s i v e l y in recent years (1-4). R e f e r e n c e electrodes based on the P d - H system h a v e been used by several w o r k e r s (5-7). Ives and J a n z (8) h a v e r e v i e w e d the l i t e r a t u r e on the p a l l a d i u m - h y d r o g e n system up to 1961. At that time, differences in the e x p e r i m e n t a l results and t h ei r i n t e r p r e t a t i o n w e r e apparent; these differences still persist. One of the m a i n points in contention is the potential d e t e r m i n i n g m e c h a n i s m for the observed ~-50 m v plateau of the P d - H electrode. Ho ar e (1) fo u n d that p a l l a d i u m will absorb h y d r o gen from aqueous acid solutions up to the atom ratio H / P d - ~ 0..03, or a p p r o x i m a t e l y to the limit of the ~-phase. 1 He attributes the steady potential of ~-50 m v to the ( P d - H ) ~ mixture. To explain t h e continuity of the ~-50 m y potential up to the concentration H / P d ~ 0.36, a m i x e d potential was postulated due to the simultaneous presence of the ~ and ~ phases, w i t h the a phases p r e d o m i n a t i n g (1). Equations w e r e d e r i v e d to show that the W50 m v p l a t e a u is due to the pure ~ phase at its m a x i m u m concentration, H / P d ~ 0.03. F l a n a g a n and Lewis (2) h a v e f o u n d that th e absorption of h y d r o g e n f r o m acid solutions does not stop at the ~ phase limit, but proceeds on the a ~- ~ region, and finally to the pure ~ phase [later w o r k by H o a r e (9) also confirms this fact]. T h e y a tt r ib u t e the ~ 5 9 m v plateau to the presence of the t w o - p h a s e region, and the subsequent drop to zero volts to the pure phase. The drop in potential f r o m the initial v a l u e to the ~ 5 0 m v ptateau is a t t r i b u t e d to the presence of the pure a phase. Both F l a n a g a n and Lewis and Hoare and coworkers used r e l a t i v e resistance m e a s u r e m e n t s to d e t e r m i n e the H / P d ratio. Cathodically charged p a l l a d i u m - h y d r o g e n electrodes h a v e been studied by several w o r k e r s (10-12). Th ei r general conclusions or implications are that the potential rem ai n s constant over the entire t w o - p h a s e (~ ~- ~) region, and is a function of composition in the p u r e ~ and p u r e ~ regions. More recent w o r k on the p a l l a d i u m - h y d r o g e n system has been done by A b e n and B u r g e r (3) using polycrystalline x - r a y diffraction to detect the phase present at the surface of the p a l l a d i u m after absorption of H2 f r o m aqueous acid solutions. T h e i r w o r k supports the v i e w that the potential is d ep en d en t on composition in the p u r e ~ and ~ phases, but is i n d e p e n d e n t of composition in the m i x e d , ~phase region.
1 The phases of the palladium-hydrogen alloy are determined by t h e a m o u n t of d i s t e n t i o n i n t h e l a t t i c e p a r a m e t e r of p u r e p a l l a d i u m . T h e l a t t i c e p a r a m e t e r o f p u r e P d is 3.883A, w h i l e t h a t of t h e ce p h a s e is 3.886A, a n d t h a t of t h e ~ p h a s e i s 4.032A.

The pressure vs. composition isotherms and heats of solution for h y d r o g e n gas in e q u i l i b r i u m w i t h pallad i u m m e t a l h a v e been d e t e r m i n e d most r e l i a b l y by Gillespie and co w o r k er s (13, 14). A successful theoretical t r e a t m e n t of this system w h i ch supports the idea that h y d r o g e n forms a homogeneous solid solution w i t h p a l l a d i u m has been given by L a c h e r (15). T h e object of t h e f o l l o w i n g study was to p r e pa r e a p a l l a d i u m h y d r o g e n r e f e r e n c e electrode by cathodic occlusion of hydrogen. Such r e f e r e n c e electrodes h a v e been p r e p a r e d by absorption of gaseous h y d r o g e n from acid solutions, and w e r e given the n a m e ~-Pd r e f e r ence electrodes (5, 16). Th e attempts to p r e p a r e such an electrode electrolytically led to a r e - e x a m i n a t i o n of the potential vs. composition relationship for this system. In this study a gas c h r o m a t o g r a p h was used to analyze for the h y d r o g e n content in the palladium. The w o r k was then e x t e n d e d to include potential vs. t e m p e r a t u r e m e a s u r e m e n t s for p a l l a d i u m - h y d r o g e n alloys produced by cathodic charging, and also by absorption of gaseous h y d r o g e n f r o m acid solutions.

Apparatus
T h e cell used was a simple H - t y p e cell w i t h the two c o m p a r t m e n t s separated by a fine porosity glass frit. N i t r o g e n or h e l i u m was supplied both above and below the solution l ev el in the c o m p a r t m e n t that contained the Pd test electrode. A p r e s a t u r a t o r for the h y d r o g e n supplied to the H ~ / P t r e f e r e n c e electrode was used. The entire apparatus was i m m e r s e d in a t h e r m o s t a t i cally controlled t e m p e r a t u r e bath at 24.8 ~ 0.1~ The electrolyte was 1N perchloric acid, m a d e up w i t h w a t e r f r o m a B a r n s t e a d h i g h - p u r i t y distillation apparatus and 70% perchloric acid (G. F. S m i t h and C o m p a n y ) . F o r potential vs. composition measurements, the pall a d i u m electrodes w e r e m a d e using 0.0125 in. d i a m e t e r w i r e ( E n g e l h a r d Industries) spot w e l d e d to p l a t i n u m leads of 0.025 in. d i a m e t e r at both ends. These p l a t i n u m leads w e r e then inserted t h r o u g h a r u b b e r septum (injection gasket) up to the P t to P d spot welds, giving a p a l l a d i u m loop electrode with two contacts. T h e septum was t h e n force fitted into the end of a glass sleeve w h i ch contained the lead that connected the p a l l a d i u m electrode to the testing apparatus. F or the t e m p e r a t u r e dependence m e a s u r e m e n t s and r e f e r e n c e electrode experiments, a p a l l a d i u m w i r e a p p r o x i m a t e l y 4 cm long and 0.0125 in. in d i a m e t e r was spot w e l d e d to a p l a t i n u m lead at one end. The p l a t i n u m lead was then sealed in soft glass, up to, and just including, the spot weld. The straight, exposed p a l l a d i u m w i r e was then sheathed in a glass capillary w h i c h could serve as a luggin capillary. T h e m e a s u r i n g i n s t r u m e n t s used w e r e as follows: f o r potential difference m easu r em en t s, a K e i t h l e y elec865

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866

JOURNAL

OF

THE

ELECTROCHEMICAL

SOCIETY

August

1965

t r o m e t e r (--+0.5 m v ) as w e l l as a p o t e n t i o m e t e r capable of r e a d i n g m y ; for q u a n t i t y of h y d r o g e n in p a l l a d i u m an A e r o g r a p h A - 9 0 - P 2 gas c h r o m a t o g r a p h capable of detecting less than 1 #1 of gaseous H2 in a c a r r i e r stream of nitrogen. The p a l l a d i u m in the loop electrodes was w e i g h e d to the n e a r e s t t e n t h m i l l i g r a m on a Mettler g r a m m a t i c balance. A c o n s t a n t - c u r r e n t source was m a d e by using a P h i l b r i c k R100B p o w e r supply (+300v, --300v) in series w i t h precision r e sistors.

Platinization of the P t / H 2 r e f e r e n c e electrode was carried out according to a p r o c e d u r e described by Ives and J a n z (8). 'The c u r r e n t density used for platinization was a p p r o x i m a t e l y 15 m a / c m ~. Palladization of the p a l l a d i u m electrodes, w h e n done, was carried out at c u r r e n t densities of a p p r o x i m a t e l y 30 m a / c m 2. Palladizing solution was p r e p a r e d according to a procedure g i v en by Bates (17).

Discussion and Experimental Results

The p o t en t i al of + 5 0 m v for a P d - H electrode in the t w o - p h a s e region r e q u i r e s a t h e r m o d y n a m i c e xplanation. It is held in the presence of dissolved h y drogen (P = 1 atm) and in the absence of dissolved hydrogen. It is evident that the P d - H alloy supplies its own h y d r o g e n for the potential d e t e r m i n i n g r e action at the activity prescribed by the phase or phases present. F l a n a g a n and Lewis (2) propose the following half reactions for the system w h e n absorbing h y d r o g e n f r o m solution. x H : y P d + H + + e - -> (x + 1 ) H : y P d Pd electrode [1] 1/2 H2-> H + + e - P t electrode [2]

Procedure
Potential vs. co~npos~tion m e a s u r e m e n t s . - - T h e palladium loop electrodes w e r e charged w i t h h y d r o g e n by cathodizing t h e m at a constant c u r r e n t of either 30 or 150 ~a ( c u r r e n t densities of a p p r o x i m a t e l y 60 and 300 /za/cm2). B e t w e e n 60% and 90% of t h e h y d r o g e n liberated by this cathodization was occluded in the p a l l a d i u m lattice. T h e potential of the electrode thus charged was m e a s u r e d in nitrogen swept solution vs. a n o r m a l h y d r o g e n electrode. A f t e r the potential was tested, t h e electrode was r e m o v e d f r o m the cell, rinsed in distilled w a t e r as r a p i d l y as possible, and the septum holding the Pd loop w a s then pried out of the glass sleeve. T h e septum was then inserted in a specially m a d e injection port on the gas chromatograph, and 6v a.c. was applied across the p l a t i n u m leads after t h e y had been l o w e r e d sufficiently to avoid heating the septurn. The 6v a.c. was enough to cause the p a l l ad i u m loop to glow r ed and eject its h y d r o g e n into the c a r r i e r gas stream. Various methods of p r e t r e a t m e n t of the p a ll ad i u m electrodes w e r e tried. They included annealing in a gas-air flame, an n e a l in g by electrical heating, i m m e r sion in boiling concentrated nitric acid, and anodization. It has been observed that charging the p a ll ad i u m electrodes electrolytically leads to h i g h e r concentrations of h y d r o g e n at the surface than in t h e bulk (2). To minimize this possibility, low c u r r e n t densities w e r e used, and an anodization p r o c e d u r e was deve l o p ed which depends on the diffusion of the bulk h y d r o g e n tOr the surface to r e l i e v e concentration gradients. The anodization p r o c e d u r e simply involves r e v e r s i n g the c u r r e n t for a short time i n t e r v a l followed by a m e a s u r e m e n t of the rest potential. This process was r e p e a t e d until no change in potential occurred with the anodization. T e m p e r a t u r e dependence m e a s u r e m e n t s w e r e carried out by first getting an electrode to exhibit the + 5 0 m v plateau, at 25~ and then raising or l o w e r i n g the bath t e m p e r a t u r e in 5~ steps. T h e system was allowed to r e m a i n at each t e m p e r a t u r e at least 1/2 hr after achieving a steady potential. The t e m p e r a t u r e bath was t h e r m o s t a t i c a l l y controlled at all values to 176 The stability of the electrode was tested prior to variations in the t e m p e r a t u r e by l e a v i n g the electrode on open circuit in solutions s w e p t w i t h inert gases for periods of 8-10 hr. A f t e r the w h o l e t e m p e r a ture r a n g e f r o m 25 ~ to 50~ and f r o m 25 ~ to 0~ was examined, the t e m p e r a t u r e was r e t u r n e d to 25~ and the potential and hence stability of the electrode w e r e again checked. T h e t e m p e r a t u r e dependence of the plateau potential was also m e a s u r e d for electrodes of the configuration described previously, w h i le absorbing gaseous h y d r o g e n f r o m solution at pressure equal to 1 atm. In these investigations, no l o n g - t e r m stability tests w e r e made prior to v a r i a t i o n of th e t e m p e r a t u r e . Th e electrode potential was allowed to r e a c h a steady state w i t h h y d r o g e n gas at 1 atm pressure, and t e m p e r a t u r e variations w e r e started promptly. To test the electrode response to solutions at diff e r e n t h y d r o g e n ion concentrations the electrode was r e m o v e d f r o m the cell (capillary included) and the electrolyte in the cell was t h o r o u g h l y flushed out and replaced with el e c tr o ly te of different h y d r o g e n ion concentration. W h il e the electrolyte in the cell was being changed, the p a l l a d i u m - h y d r o g e n electrode was rinsed t h o r o u g h l y w i t h and stored in the n e w solution.

They give as the net reaction, the sum of these two half reactions. xH: y P d + 1/2 H2--> (x + 1)H: y P d [3]

They t h e n go on to co m p ar e the free energies for the net reaction w i t h t h e f r e e e n e r g y change calculated f r o m the e q u i l i b r i u m gas phase isothermal data of Gillespie (13, 14). However, the eq u i l i b r i u m pressure of h y d r o g e n gas in contact with p al l ad i u m at 25~ is 0.0202 atm, and the only t e r m that involves hydrogen gas in Eq. [3] is that w h i ch derives from the h y d r o g e n r e f e r e n c e electrode, w h i ch is at P = 1 atm. The connection b e t w e e n AG as calculated f r o m the gas phase data of Gillespie and the net reaction Eq. [3] given by F l a n a g a n and Lewis is not quite clear. An alternate, and m o r e precise method of treating this system is to a r r i v e at a Nernst equation based on Eq. [3]. This equation will be accepted as the potential d e t e r m i n i n g mechanism, regardless of the phase or phases present at the surface of the P d - H alloy. For the n et reaction, Eq. [3], AG m ay be w r i t t e n AG -~ (x + 1)~H (m) + y / z p d ( m ) ' - 1/2/r - - y/~pd ( m ) - - X/OH ( m )

[4]

according to AG = Zn~,i prod. -- Znj~j react. Th e symbols a r e : /zH(m) ~ chemical potential of H atoms in the Pd lattice; #Pd z chemical potential of Pd atoms; and ~i2 <g) = chemical potential of H2 in the gas phase. Upon subtracting terms 1 aG = ~H~m) - - - 2 - ~H2(g) [5]

which cl ear l y indicates the H atoms in the P d lattice as a part of the potential d e t e r m i n i n g mechanism. It remains to find an expression for # H ( m ) . T h e r e is good reason to b e l i e v e that a reaction of the type y P d : x H = yPd: ( x - - 2 ) H 2H = H2 + 2H

takes place at the surface of the P d - H alloy (18). The P d - H alloy w o u l d then be in e q u i l i b r i u m with H2 only w h e n the pressure of h y d r o g e n is given by the isotherms d e t e r m i n e d by Gillespie. These facts lead to an expression for ~ ( ~ ) since by conditions for e qui l i b r i u m the following relationships must be satisfied
/~H ( m ) ~ /IH(g) [6]

w h e r e ~ H (g) : chemical potential of h y d r o g e n atoms in the h y d r o g e n gas in e q u i l i b r i u m with the P d - H alloy.

~ H (g) ~ ~H2 (g) [7]

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Vol. 112, No. 8

PROPERTIES

OF

A Pd-tt

ELECTRODE

867

a n d #n2 (g) is t h e c h e m i c a l p o t e n t i a l of h y d r o g e n g a s a t t h e e q u i l i b r i u m p r e s s u r e , P = P'H2. T h i s p r e s s u r e is 1 a t m o n l y w h e n t h e a t o m r a t i o H / P d = 0.69. Now t~H~(g) ~ #H2 ~ -]-

RTlnP'H2

[8]

9C

T h e r e f o r e , b y e q u a t i n g Eq. [6] a n d Eq. [7] ~H (m)

=

Vz~H2(g)

[9]

E
. 80

a n d finally, b y s u b s t i t u t i n g Eq. [8] i n Eq. [9], ~~ 2

~H (m) = -~- 9

RT
2

I n P'II2

[10]

U.I '0 Z Ld nL.d I.L

F o r t h e n e t r e a c t i o n , AG m a y n o w b e w r i t t e n e x p l i c i t l y ~On2 AG - - - -}2
or

u_ 7 0 d

RT
2

I n P'H2

t~H2o 2

--

RT
2

In PH2 [11]

Ca
U.I

AG =

RT
2

In (P'n2) ----

RT
2

~ ~o i n P~2 [12]
| o
i ,

T h e l a s t t e r m i n Eq. [12] r e f e r s to t h e n o r m a l h y d r o gen reference electrode. When corrected for the part i a l p r e s s u r e of w a t e r , Eq. [12] r e a d s AG =
where

50
, i i I i i , , | , , , , !

0.01

0.02

0.05

RT
2

In (P'H2) - - - - l n 2

RT

( PBAR-- P'H20 )
760

ATOM

RATIO, H / P d

[13]
Fig. 1. Potential difference between a normal hydrogen electrode and a palladium-hydrogen electrode as a function of composition, to the limit of the ~ phase. 9 Experimental points; solid line predicted by Eq. [22] (temperature, 25~

PBAR is t h e b a r o m e t r i c p r e s s u r e , a n d P'H20 is t h e p a r t i a l p r e s s u r e of w a t e r , b o t h i n m m Hg. S i n c e AG = - - n F E , w e g e t t h e N e r n s t e q u a t i o n

-In 2F

RT

RT P'H2 -t- ~

( PBAR-- P'H20 )
In 760

[14]

or a l t e r n a t e l y w r i t t e n E --

RT ~-

l n ( P ' H 2 ) 1/2 +

-7

RT i n ( PBAR--P'H20 ) 1/2
760
[15]

where ~ refers to the potential difference between the palladium-hydrogen electrode and the normal hydrogen reference electrode. In this derivation, the gass o l i d e q u i l i b r i u m d a t a w e r e u s e d o n l y as a m e a n s t o calculate an expression for ~(m). Gas-solid equilibr i u m does n o t e x i s t i n t h e e x p e r i m e n t a l c o n d i t i o n s e m p l o y e d i n t h i s s t u d y , or i n o t h e r s t u d i e s , e x c e p t w h e n t h e H / P d r a t i o r e a c h e s 0.69, a t a h y d r o g e n p r e s s u r e of 1 arm. T h e e s t a b l i s h m e n t of t h e s t e a d y p o t e n t i a l r e l i e s u p o n t h e e x c h a n g e of h y d r o g e n a t o m s i n t h e l a t t i c e w i t h h y d r o g e n ions i n s o l u t i o n , a c c o r d i n g to Eq. [1]. T h e a c t i v i t y of t h e h y d r o g e n i n t h e p a l l a d i u m , as d e r i v e d b y t h e p r e c e d i n g t h e r m o d y n a m i c r o u t e , w a s f o u n d to b e a c o n s t a n t i n t h e t w o p h a s e region. F r o m Eq. [15] i t is p o s s i b l e t o d e r i v e e q u a t i o n s p r e d i c t i n g t h e t e m p e r a t u r e d e p e n d e n c e of t h e p l a t e a u p o t e n t i a l a n d t h e d e p e n d e n c e of t h e p o t e n t i a l o n c o m p o s i t i o n of t h e e l e c t r o d e i n t h e a p h a s e a t a g i v e n temperature. These equations are developed in the following sections and are compared with experimental results.

T h e a t o m r a t i o w a s c a l c u l a t e d as t h e b u l k H / P d r a t i o , w i t h a p r o p a g a t e d r e l a t i v e e r r o r of at worst. The samples used in determining this segment of t h e c u r v e w e r e c h a r g e d a t a c u r r e n t d e n s i t y of ,-~ 60# a m p / c m 2 w h i c h s h o u l d e n s u r e a s m a l l c o n c e n tration gradient between the surface and the interior of t h e m e t a l . E q u a t i o n [15] c a n b e e x p a n d e d t o s h o w t h e p o t e n t i a l as a f u n c t i o n of c o m p o s i t i o n if o n e k n o w s h o w t h e p r e s s u r e v a r i e s as a f u n c t i o n of c o m p o s i t i o n i n t h e p h a s e . T a b l e s of e q u i l i b r i u m h y d r o g e n p r e s s u r e as a f u n c t i o n of c o m p o s i t i o n a t 30~ a r e g i v e n b y G i l l e s p i e a n d H a l l (13), b u t M o o n (19) g i v e s a p h e n o m e n o l o g i c a l t r e a t m e n t w h i c h a l l o w s o n e to c a l c u l a t e t h e e q u i l i b r i u m p r e s s u r e as a f u n c t i o n of t e m p e r a t u r e a n d composition. These equations, which are valid only in the ~ phase region, are

p:/2
l o g \--~--- ) = --logK + ~r [17] [18] [19] l o g K = - - 4.200 + 521.9/T fl = - - 9 2 6 / ( T - 215)

K is t h e e q u i l i b r i u m c o n s t a n t f o r t h e r e a c t i o n
1/~H2(g) -~-

(()

P d (s) = Pd(1/r) H (s'a)

s h o w s t h e p o t e n t i a l vs. c o m p o s i t i o n c u r v e f o r a p a l l a d i u m - h y d r o g e n e l e c t r o d e i n t h e p u r e a r e g i o n a t 25~ T h e p o t e n t i a l is d e c i d e d l y a f u n c t i o n of t h e a t o m r a tio, H / P d , a n d a p p r o a c h e s a v a l u e of + 52 to + 53 m v , as t h e l i m i t of t h e a p h a s e is r e a c h e d . P r e v i o u s m e t h o d s of m e a s u r i n g t h e a t o m r a t i o w e r e n o t c a p a b l e of s u c h a c c u r a c y , p r e s u m a b l y b e c a u s e t h e l i f e t i m e of t h e a p h a s e is so s h o r t w h e n t h e p a l l a d i u m is c h a r g e d b y a b s o r p t i o n of g a s e o u s h y d r o g e n . X - r a y a n a l y s i s (3) h a s e s t a b l i s h e d t h e p r e s e n c e of t h e , p h a s e d u r ing the descent to +50 mv, but the bulk H/Pd ratio was not obtained by this method.

Potential as a Sunction of composition.--Figure 1

w h e r e P - - e q u i l i b r i u m p r e s s u r e of h y d r o g e n , i n m m Hg, a n d r a t o m r a t i o , H / P d . C o n v e r t i n g to p r e s s u r e in atmospheres yields l o g Katm = - - 2.760 + 521.9/T [20]

B y s u b s t i t u t i n g Eq. [19] a n d [20] i n t o Eq. [17], a n e q u a t i o n f o r t h e e q u i l i b r i u m p r e s s u r e of h y d r o g e n results. For T = 298~

l o g P1/2atm ~ 1 . 0 0 9 - 11.15 r + l o g r

[21]

E q u a t i o n [21] m a y n o w b e s u b s t i t u t e d i n t o Eq. [15], t h e r i g h t - h a n d s i d e of Eq. [21] r e p l a c i n g t h e t e r m l n ( P ' s 2 ) 1/2 i n Eq. [15], a f t e r c h a n g i n g t h e b a s e of the logarithm in the latter term. The resulting equat i o n is

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868
I00 9(:]

J O U R N A L OF THE E L E C T R O C H E M I C A L SOCIETY

August 1965

~ 6c
a_ 5C

;.

..-

o_ 2C

\
,'o ~'.o 3.o' 4'.0 d.o 6,o' 7.'0
.~TOM RATIO, H / P d , xlO

Fig. 2 . Complete potential v s . composition curve for a palladiumhydrogen electrode (temperature, 25~ E ~ --0.05916 (1.0.09-11.15 r -t- log r) -t- 0.5916 log / PBAR~ P ' H 2 0 ~1/2 / 760 [22]

for T = 298~ In Fig. 1, the solid c u r v e is the plot of Eq. [22] for values of r in the i n t e r v a l 0.0025 to 0.03. T h e a g r e e m e n t b e t w e e n the o b s e r v e d values and those p red i ct ed by Eq. [22] is good, and provides substance to the t h e r m o d y n a m i c a r g u m e n t s advanced. A t the limit of the ~ phase Eq. [22] predicts a v a l u e of ~ = W 49.8 mv. T h e v a l u e for E in the t w o - p h a s e region calculated by using Eq. [15] is also ~- 49.8 mv. Thus, the two equations predict the same v a l u e of E at the point w h e r e the physical situation demands that their m a t h e m a t i c a l descriptions coincide. The complete p o te n t ia l- c o m p o s i ti o n c u r v e is shown in Fig. 2. The potential was found to be constant in the t w o - p h a s e region up to the concentration H / P d = 0.52. The t o l er an c e in the potential values was t ak en to be 50 -+- 2 mv, in accord w i t h p r e v i o u s w o r k e r s (2, 3). E q u a t i o n [15] predicts a constant potential over the entire two phase (a + fi) region. A t constant t e m perature, the only v a r i a b l e to appear in this equation is P'H2, w h i c h was found to be constant in the t w o phase region by Gillespie and Hall (13). The pressure of h y d r o g e n gas in e q u i l i b r i u m w i t h a p a l l a d i u m - h y drogen alloy in the t w o - p h a s e region at 25~ can be found f r o m Eq. [23], due to Gillespie. Substitution of this v a l u e of the e q u i l i b r i u m pressure into Eq. [15] yields a v a l u e of -F 49.8 m v as the potential in the t w o phase region at 25~ F o r some e x p e r i m e n t a l points beyond the ratio H / P d = 0.4 it was necessary to anodize the electrodes to r e m o v e excess surface hydrogen. 'The anodization was done fo r convenience, since, if one is w i l l i n g to w a i t long enough, the simultaneous process of i n w a r d diffusion of hydrogen, and diffusion of h y d r o g e n into the electrolyte will result in a surface concentration w h i ch is v e r y close to the bulk concentration. In order to achieve H / P d ratios of 0.4 or greater, the c u r r e n t d e n sity was increased to 300 # a / c m 2. To j u s t i f y q u a n t i t a t i v e l y the anodization technique, solutions for the diffusion of h y d r o g e n in p a l l a d i u m w e r e w o r k e d out. The b o u n d a r y conditions contain the assumption that the anodization r e m o v e d all the h y drogen f r o m the m e t a l to a radius consistent w i t h the total n u m b e r of anodic coulombs passed. A diffusion equation for the system, and the diffusion coefficient for h y d r o g e n in p a l l a d i u m m a y be r e a d i l y found (20). A solution of the equation for a typical case y i e l d e d the t i m e necessary for the surface concentration to re a c h 99% of the bulk concentration to be of t h e order of m a g n i t u d e of 10 -2 sec. Thus, the anodization p r o c e d u r e can be justified on the grounds that the bulk H / P d ratio establishes itself v e r y r a p i d l y at the surface aft er the cessation of anodic current.

The b r e a k i n g point for the two phase limit was not determined, but points w h i c h lie in the pure /~ phase w e r e found. In Fig. 2, the last point found in t h e t w o phase region ( H / P d ~ 0.52) was joined by a smoothly descending cu r v e (shown by t h e dotted line) with t h e t h r e e points found in the fi phase only for the sake of continuity. I t was f o u n d to be difficult to charge samples to a H / P d ratio g r eat er than 0.64 at the c u r r e n t densities employed. A probable e x p l a n a tion for this fact is that h y d r o g e n in the m et al is lost during the t i m e i n t e r v a l b e t w e e n cessation of the cathodic c u r r e n t and analysis of the sample. The anodization t ech n i q u e was not used w h e n studying the /~ phase potential behavior. In these e x p e r i m e n t s the solution in which t he pall a d i u m electrode was tested was constantly sw ep t with nitrogen. T h e r e was effectively no means of p r e v e n t i n g h y d r o g e n dissolved in the p a l l a d i u m from establishing its e q u i l i b r i u m concentration in the electrolyte solution. 'This process m a n i f e s t e d itself in a v e r y slow rise in potential w i t h time for electrodes that w e r e in the/~ phase. Therefore, it is not necessary to i n v o k e reasons for /~ phase instability in cathodically charged p al l ad i u m h y d r o g e n w h e n no h y d r o g e n is dissolved in the solution, since transport processes are sufficient to explain the loss of hydrogen. Th e g en er al conclusions d r a w n f r o m the potentialcomposition data are that the potential is dependent upon the composition of the electrode in the p u r e and pure ~ phase, and i n d e p e n d e n t of composition in the ~ ~- /~ region. These conclusions agree w i t h those of other workers, most r e c e n t l y A b e n and B u r g e r (3), and F l a n a g e n and Lewis (2). Potential as a function of temperature.--Figure 3 shows the t e m p e r a t u r e dependence of the cathodically charged p a l l a d i u m h y d r o g e n electrodes. The e x p e r i m e n t a l b e h a v i o r is v e r y close to being linear, w i t h a slope of - - 0.65 m v / ~ The data of Ratchford and Castellan (21) are included in Fig. 3. Their t e m p e r a t u r e d e p e n d e n c e m e a s u r e m e n t s w e r e p e r f o r m e d while the p a l l a d i u m was absorbing h y d r o g e n from solution, and the t e m p e r a t u r e r an g e studied was from 20 ~ to 60~ By use of their empirical equation E = 0.06309 - - 0.0005057(T-273.16) their values m a y be e x t e n d e d to 0~ It is ev i d en t that the slopes of the two different determinations do not agree. To test the possibility that electrode construction m ay h a v e been responsible for this difference in slope, gas-phase absorption e x p e r i ments in aqueous solution w e r e carried out. Results

6C

55

z ~.5o

~_4a
z

40

35

TEMPERATURE ~C

Fig. 3. Potential as a function of temperature for a palladium hydrogen electrode. 9 Experimental, electrolytically charged; 4, data of Ratchford and Castellan; solid line predicted by Eq. [24].

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Vol. 112, No. 8

PROPERTIES

O F A Pd-H

ELECTRODE

869

are shown in Fig. 4. The slopes of the straight lines are in good agreement, and the potential values at any giv en t e m p e r a t u r e are within 1 m v of the predicted curve. The t e m p e r a t u r e dependence of th e potential of a t w o - p h a s e p a l l a d i u m h y d r o g e n electrode can be d er i v e d f r o m Eq. [15]. Gillespie and G a l s t a u n (14) give an equation w h i c h fits the t w o - p h a s e e q u i l i b r i u m pressures for t h e p a ll a d iu m h y d r o g e n system as a function of t e m p e r a t u r e .
log Patm ~

4.6018 - - 1877.82/T

[23]

Substitution of this expression into Eq. [15] yields E 2.393 RT 2F ( 4 . 6 0 1 8 - 1877.82/T)

PBAR --

RT -4- - - ~ In (

-~-~

P'H20[

[24]

Inspection shows that this is a linear equation in T, w i t h the exception of the t e r m that involves the p a r tial pressure of water. Values calculated f r o m Eq. [24] are plotted in Fig. 3 as a comparison w i t h the various experiments. In the range 25 ~ < T < 50~ the a g r e e m e n t b e t w e e n Eq. [24] and e x p e r i m e n t is quite good for the case w h e r e p a l l a d i u m was absorbing h y d r o g e n dissolved in solution. T h e a g r e e m e n t b e t w e e n Eq. [24] and the data of R at ch f o rd and Castellan gets poorer as the t e m p e r a t u r e progresses to 0~ A c c o r d in g to Gillespie and Galstaun, t h e equation t h a t gives the e q u i l i b r i u m pressure of h y d r o g e n in the t w o - p h a s e region is in e r r o r below 30~ The e r r o r becomes l a r g e r as the t e m p e r a t u r e gets l o w e r since their straight line approximates a c u r v e in this region. The e q u i l i b r i u m pressure equation predicts 4.05 m m Hg for 0~ and the observed e q u i l i b r i u m pressure was 3.56 m m Hg. If this e x p e r i m e n t a l l y observed pressure i s substit uted into Eq. [15]. the predicted v a l u e of E is -F 63.14 my. R at ch fo rd and Castellan's empirical equation has -F 63.09 m y as its 0~ value. T h e a g r e e m e n t h e r e is excellent. The t h e r m o d y n a m i c a r g u m e n t s advanced h a v e been r e m a r k a b l y successful in accounting for the t e m p e r a -

t u r e dependence of the p a l l a d i u m - h y d r o g e n electrode w h i l e it is absorbing gaseous hydrogen. Th e a g r e e m e n t b e t w e e n t h e o r y and e x p e r i m e n t is not quite as good for t h e case of cathodically charged p a l l a d i u m - h y d r o gen electrodes, although it is f ar f r o m a failure. It is quite probable t h a t t h e discrepancies b e t w e e n the two e x p e r i m e n t a l situations are due to n o n r e v e r s i b i l i t y in the desorption process w h i c h m u s t take place in or de r to h a v e the cathodically charged electrodes establish a potential. P h e n o m e n a such as rift occlusion of h y d r o gen and hysteresis effects in the pressure vs. t e m p e r ature relationship of the p a l l a d i u m - h y d r o g e n alloy are possible sources of n o n r e v e r s i b l e b e h a v i o r (22) w hi c h m a y alter the t e m p e r a t u r e dependence of the potential for cathodically charged electrodes. These p h e n o m e n a w o u l d h a v e a less pronounced effect for an electrode that is absorbing h y d r o g e n f r o m the gas phase. No p H dependence could be found for t w o - p h a s e p a l l a d i u m h y d r o g e n electrodes w h e n tested against a h y d r o g e n electrode. Electrolytes that w e r e tested w e r e 2N, 1N, 0.1N, and 0.001N perchloric acid. T h e P a l l a d i u m - H y d r o g e n Reference Electrode T h e p r eced i n g w o r k was done w i t h the object of d e v e l o p i n g a p a l l a d i u m - h y d r o g e n r e f e r e n c e electrode by electrochemical means. O t h er w o r k e r s (5, 16) h a v e m a d e such an electrode by gas charging methods. It has been called the a - p a l l a d i u m r e f e r e n c e electrode, since the + 5 0 m y potential is characteristic of the concentration limit of the a phase. In practice, the " a - p a l l a d i u m " r e f e r e n c e electrode actually has a composition in the t w o - p h a s e region w h e r e the potential is essentially i n d e p e n d e n t of the H / P d ratio. Th e electrode was constructed ex act l y the same w a y as those used for the t e m p e r a t u r e d e p e n d e n c e m e a s urements. H y d r o g e n was supplied to the p a l l a d i u m by constant c u r r e n t electrolysis of c u r r e n t density 75 ~ a / c m 2. These electrodes w e r e palladized at a c u r r e n t density of 15 m a / c m 2 for 2 rain, prior to charging with hydrogen. If the electrodes displayed potentials l o w e r than + 5 0 m v after charging for a period of time necessary to give a H / P d ratio of 0.5 (based on c u r r e n t sorption efficiency of 60%), they w e r e anodized according to the p r o c e d u r e described previously. A n odization, if necessary, r e - e s t a b l i s h e d the + 5 0 m v plateau potential, and t h e electrode was then inserted into a capillary sheath to m i n i m i z e t h e loss of h y d r o gen by diffusion. S u c h an electrode could be k e p t for periods of 24 hr in n i t r o g e n sw ep t solutions w i t h only negligible changes in potential. F o r longer periods of time the potential was found to d r i f t one or 2 m v but it could be restored to + 5 0 m v by cathodization at t h e same c u r r e n t density r e q u i r e d for charging. Two disadvantages of t h e p a l l a d i u m h y d r o g e n r e f erence electrode as described h e r e are: 1. P r e p a r a t i o n : long electrolysis times are necessary due to such l o w currents. 2. Imprecision in the potential value. (Some w o r k ers h a v e r e p o r t e d a v a l u e of +49.5 my, and others a v a l u e of +50.4 my.) F o r w o r k that does not r e q u i r e such g r eat accuracy, the potential m a y be t ak e n as 50 ___ 1 my. It is also necessary to check the initial potential v a l u e against a n o r m a l h y d r o g e n electrode, or some suitable r e f e r e n c e electrode. T h e p r i m e a d v a n t a g e of this electrode is that it has the same p t I response as a Pt / H 2 electrode, but m a y be used in h y d r o g e n f r e e solutions. T h e r e are se ve r a l e x p e r i m e n t a l situations w h e r e dissolved m o l e c u l a r h y drogen must be k e p t out of a test electrode c o m p a r t m e n t and elaborate m et h o d s and apparatus design are usually necessary to accomplish this. The use of a t w o phase p a l l a d i u m - h y d r o g e n electrode in a luggin cap i l l ar y w o u l d e l i m i n a t e the need of separating the r e f e r e n c e electrode c o m p a r t m e n t f r o m the test elect r o d e c o m p a r t m e n t , and t h e r e f o r e g r e a t l y simplify cell designs.

50

E
o Z 45 l.J u_ u_

~ 4o
VZ
LU I--0 35

3C ZO

30

40

50

TEMPERATURE ~

Fig. 4. Potential as a function of temperature for a palladiumhydrogen electrode while absorbing hydrogen from a solution. I~, This study; A , data of Ratchford and Castellan; solid line predicted by Eq. [24].

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870

JOURNAL

OF THE ELECTROCHEMICAL

SOCIETY

A u g u s t 1965

Acknowledgment This work was i n part supported by the Directorate of Chemical Sciences, Air Force Office of Scientific Research, u n d e r G r a n t AFOSR-151-63. The authors also wish to t h a n k The Electrochemical Society for its support in the form of the Electrochemical Society S u m m e r Fellowship, (1964). Manuscript received Jan. 19, 1965; revised m a n u script received April 1, 1965. A n y discussion of this paper will appear in a Discussion Section to be published in the J u n e 1966 JOURNAL. REFERENCES 1. S. Schuldiner, G. Castellan, and J. P. Hoare, J. Chem. Phys., 28, 16 (1958). 2. T. B. F l a n a g e n and F. A. Lewis, Trans. Faraday Soc., 55, 1409 (1959). 3. P. C. A b e n and W. G. Burger, ibid., 58, 1989 (1962). 4. J. P. Hoare and S. Schuldiner, J. Phys. Chem., 61, 399(1957). 5. J. P. Hoare, This Journal, 110, 245 (1963). 6. M. F l e i s c h m a n n and H. Thirsk, Trans. Faraday Soc., 51, 71 (1955). 7. S. Schuldiner and J. P. Hoare, Can. J. Chem., 37, 228 (1959).

8. D. J. Ives and G. J. Janz, "Reference Electrodes," Academic Press, New York (1961). 9. J. P. Hoare, J. Phys. Chem., 64, 1780 (1960). 10. A. F~cumkin a n d N. Aladjalova, Acta Physicochem. URSS, 19, 1 (1944). 11. P. Nylen, Z. Elektrochem., 43, 915 (1937). 12. A. F r u m k i n , Dis'cussions Faraday Soc., 1, 137 (1947). 13. L. J. Gillespie and P. Hall, J. Am. Chem. Soc., 48, 1209 (1926). 14. L. J. Gillespie and L. S. Galstaun, ibid., 48, 1209 (1926). 15. J. R. Lacher, Ro~ Soc. London, Proc., 161, 25 (1937). 16. J. P. Hoare, Gen. Motors Eng. J., 9 [7], 14 (1962). 17. R. G. Bates, "Electrometric pH Determinations," J o h n Wiley & Sons, Inc, New York (1954). 18. T. B. F l a n a g e n and F. A. Lewis, Trans. Faraday Soc., 56, 363 (1960). 19. K. A. Moon, J. Phys. Chem., 60, 502 (1956). 20. W. Jost, "Diffusion," Academic Press, New York (1960). 21. it. J. Ratchford and G. W. Castellan, J. Phys. Chem., 62, 1123 (1958). 22. D. P. Smith, "Hydrogen in Metals," p. 95, U n i v e r sity of Chicago Press, Chicago (1948).

Technka]l
A Potentiometric Determination of Sodium in Amalgams
J. A. LeDuc, C. Lurie, and J. Kourilo

Electrochemical Research Section, Research and Development Department, M. W. Kellogg Company, New Market, New Jersey
The need for a rapid, accurate method for determ i n i n g sodium concentration i n a flowing a m a l g a m stream was realized d u r i n g a recent investigation of the ability of the sodium a m a l g a m - o x y g e n fuel cell to recover power consumed d u r i n g electrolysis of b r i n e in m e r c u r y cells. A potentiometric method was decided on and involved m e a s u r i n g the potential bet w e e n an amalgam half cell and a Hg/HgO reference cell Na (Hg),Na + INaOH (50.%) IHgO,Hg [1] The relationship between cell potential and sodium concentration was d e t e r m i n e d at 20~ using a series of a m a l g a m samples c o n t a i n i n g 0.01-0.53 w / o (weight per cent) sodium. The m e a s u r i n g system used is depicted i n Fig. 1. The a m a l g a m to be measured was admitted, to the m e a s u r i n g cell H through the stopcock at G. After the potential across the system was read the a m a l g a m was drained from the m e a s u r i n g cell H through a stopcock and another sample i n t r o duced through G. Reagent grade sodium metal and m e r c u r y purified in a laboratory-designed fractionating still were used. Sodium concentration was det e r m i n e d by reacting the a m a l g a m with an aliquot of hot hydrochloric acid of k n o w n concentration and titrating the excess acid. The potentiometric m e a s u r e ments were made with a G r a y I n s t r u m e n t C o m p a n y Model E-3040-H potentiometer. The curve ~in Fig. 2 was fitted by the method of least squares. Analysis of the data reveals that the curve can be expressed as two linear relationships log [Na] = (E--1.662)/0.105 [2] for E > 1.559v log [Na] = (E--1.624)/0.0636 [3] for E < 1.559v where E is the potential across [1]. The break in the Nernst equation plot is believed to be real within exp e r i m e n t a l uncertainty. Solution of Eq. [2] and [3] indicates that the sodium concentration at that point corresponds to NaHg114. /
F

J
-F

"-

. . . . .

Fig. 1. Experimental cell: A, sodium amalgam; B, mercury; C, mercury and mercuric oxide; D, 50% sodium hydroxide; E, 50% sodium hydroxide salt bridge; F, leads to potentiometer; G, amalgam source; H, measuring cell, I, reference cell.

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