C. A N D R A D E
Institute "Eduardo Torroja" of Construction Sciences
CSIC - Madrid - Spain
INTRODUCTION
724
Vol. 23, No. 3 CHI.)RIDE DIFFUSION,AASHTOTEST, RESISTIVH'Y 725
In t h e c a s e of p u r e d i f f u s i o n the c a l c u l a t i o n of t h e p e n e t r a t i o n
r a t e of c h l o r i d e , has b e e n m a i n l y s t u d i e d by m e a n s of e x p e r i m e n t s
a s s u m i n g e i t h e r s t e a d y - s t a t e or n o n - s t e a d y - s t a t e flow. In t h e case
of s t e a d y - s t a t e c o n d i t i o n s (1-5), u s u a l l y a t h i n d i s c of c e m e n t
paste is i n t r o d u c e d in b e t w e e n the two c h a m b e r s of a n a m e d
" d i f f u s i o n cell", and first Fick's law is a p p l i e d (6) in o r d e r to
calculate an Effective Diffusion Coeficient, D~, (diffusion
c o e f f i c i e n t in a p o r o u s medium):
dC dC(x)
-J(x) = = Dc~ [i]
dt dx
T h i s m e t h o d o l o g y p r e s e n t s some l i m i t a t i o n s w h i c h m a y be s u m a r i z e d
as follows: a) c e m e n t p a s t e and not c o n c r e t e is u s e d w h i c h can lead
to u n r e a l i s t i c results, b) it is t i m e - c o n s u m i n g and t a k e s w e e k s to
o b t a i n one result, c) a c o n s t a n t c o n c e n t r a t i o n in the c h a m b e r
c o n t a i n i n g c h l o r i d e s from the b e g i n n i n g s h o u l d be m a i n t a i n e d .
In t h e c a s e of n o n - s t a t i o n a r y c o n d i t i o n s , c o n c r e t e b l o c k s or
specimens can be u s e d w h i c h r e s u l t s in m u c h m o r e realistic
c o n d i t i o n s . T h e s e c o n c r e t e b l o c k s are m a i n t a i n e d in c o n t a c t w i t h
a s o l u t i o n of c o n s t a n t c h l o r i d e c o n c e n t r a t i o n and the c h l o r i d e
p r o f i l e a l o n g the time is measured. In this case s e c o n d F i c k ' s law
is a p p l i e d to c a l c u l a t e the, an A p p a r e n t D i f f u s i o n C o e f f i c i e n t D a
(6):
ac(x) a2c
-J(x) = = D a - .... [2]
at ax 2
T h i s t y p e of t e s t also r e s u l t s v e r y t i m e - c o n s u m i n g and m a i n t a i n s
s e v e r a l u n c e r t a i n t i e s on the r i g o r o u s a p p l i c a t i o n of F i c k ' s law.
S o m e a u t h o r s (12) r a t h e r p r e f e r to c o m p a r e c h l o r i d e p r o f i l e s t h a n
c a l c u l a t e D,.
In a d d i t i o n , in b o t h s t e a d y and n o n - s t e a d y t e s t c o n d i t i o n s , it is
not u s u a l l y c a l c u l a t e d the r e a c t i o n or a d s o r p t i o n of c h l o r i d e s by
c e m e n t phases. T h i s c i r c u n s t a n c e is c o n s i d e r e d of m i n o r i n f l u e n c e
726 C. Andrade Vol. 23, No. 3
Electrical methods
a) Electrode processes -
a.l) M e t a l d i s s o l u t i o n - w h i c h g e n e r a t e s o x y d e s at t h e a n o l y t e
(possitive electrode chamber), if the anode is an
o x i d a b l e metal, as for i n s t a n c e copper. In the c a s e of
g r a p h i t e e l e c t r o d e s the p r o c e s s w i l l be: C --> CO + CO 2.
Not o n l y w a t e r e l e c t r o l y s i s but o x i d a t i o n of Cl a l s o m a y
h a p p e n if the v o l t a g e is h i g h e n o u g h to p r o d u c e Cl 2
evolution.
CQncrete
No +
, , , - - - C I -
OH-
Na
a) DIFFUSION
Concrete
~--- CI-
No+-~,.
b) MIGRATION
Concrete (~
Y//.//I
OH-
NQ
~ - - 0H-
V/N/ "o'-
c) DIFFUSION + MIGRATION
(~) HEAT=IZ.Rohm (~
:" No+._...
0 00
b) Migration -
T r a n s f e r e n c e number -
i, %%xj
t~. . . . . . . [5]
i Z ZCX A
Movement of c a t i o n s -
An a d d i t i o n a l a s p e c t to be s t r e s s e d n o w is r e l a t e d to the
" a n o m a l o u s " D i f f u s i o n C o e f f i c i e n t t h a t is m e a s u r e d in the
c a s e of the c a t i o n s of small ionic radius, as Na and K
(i). T h i s b e h a v i o u r is v e r y w e l l d e s c r i b e d by B o c k r i s
(36) and G l a s s t o n e (37) c o n s i d e r i n g t h a t t h e s e ions
m i g r a t e solvated, that is, due to its s m a l l ionic radius,
Na and K d i f f u s e or m i g r a t e surrounded by w a t e r
m o l e c u l e s , as they n o r m a l l y are in solution. T h a t m a k e s
t h e i r m o v e m e n t m o r e d i f f i c u l t and t h e r e f o r e , D v a l u e s
s m a l l e r t h a n t h o s e of c h l o r i d e ions are r e p o r t e d (i).
3) The high voltage drop used (60v) induces heat (23)(27) which
in turn changes the flow speed.
These are:
tool
cm =. sg Cl- in the
catholite
I ~ , ! r w ,
TIME
Figure 4. Flux (J) of c h l o r i d e s leaving the c a t h o d i c chamber along
time.
734 C. Andrade Vol. 23, No. 3
e l e c t r o n e u t r a l i t y in this e x p e r i m e n t is m a i n t a i n e d by m e a n s
of the electrodic processes (gas evolution or metal
dissolution) and t h e r e f o r e counter diffusion or m e m b r a n e
e f f e c t s are not considered.
mol ZF ~E
Total flux = -J( ...... ) . . . . . . . De,CoL .... [7]
sg'cm 2 RT 1
JRT 1
De,= [8 ]
z F Ccl ~E
itj
J= [9]
nF
itcl ZF AE
= . . . . Def
t Ccl . . . .
[i0]
nF RT 1
T h i s e x p r e s s i o n r e s u l t s s i m i l a r to N e r n s t - E i n s t e i n (32) e q u a t i o n
but a p p l i e d for a single ionic species t h r o u g h the use of the
t r a n s f e r e n c e number:
RT RT itcl 1 1
Def~ A cl = [ii]
nF 2 nF 2 AE A C~Z
0.5m
Figure 5. S i m p l e r e p r e s e n t a t i o n of the cell for testing chloride
migration.
Vol. 23, No. 3 CHLORIDE DIFFUSION,AASH'ID TEST, RESISTIVITY 737
NUMERICAL EXAMPLES
Nernst-Plank equation
Cross-section area: 30 c m 2
D, = i0 -s cm2.sg -I
R 1 . 9 8 7 2 c a l ' m o l l ' ~ ~I
F = 2 3 0 6 3 cal'volt'1"eq "I
Z = 1
T h i s is t h e o r d e r of m a g n i t u d e of t h e f l u x t h a t w i l l b e r e c o r d e d
in t h i s k i n d of e x p e r i m e n t s , and a period of s e v e r a l h o u r s of
t e s t i n g a r e n e e d e d in o r d e r t o m i n i m i z e e r r o r s in m o n i t o r i n g it.
(0.5)(76.34)
to = ,= 0. 338
(o.5) (50.1)+(0.5) (76.34)+(o.2) (198)+(0.2) (50.1)
738 C. Andrade Vol. 23, No. 3
10-~ J f
10-1o
, ! , , , v r r
Nernst-Einstein equation
F i g u r e 7 shows a g r a p h i c r e p r e s e n t a t i o n of N e r n s t - E i n s t e i n e q u a t i o n
[ii] a s s u m i n g a s o l u t i o n 0.2 M N a O H plus of NaCl w i t h a c t i v i t y
v a l u e s of 0.i, 0.35 and 0.5 m o l / c m 3 and a c h l o r i d e t r a n s f e r e n c e
n u m b e r of 0.338:
DCi4C~,g) A a = 0 . 1 mol/cm 3
o a=0.3,5 ,,
x 0=0.5 ,,
10 - 4
10-5
10-e
10-7
lO-e
P
i 10 ,6' ,6' 16" (ohm .cm-1)
NERNST-EINSTEIN EQUATION
CONCLUSIONS
ACKNOWLEDGEMENTS
BIBLIOGI~PHY