Professional Documents
Culture Documents
l.
SIIBSTANCES C0NSIDERED
orrd,rion
331
CONSIDERED
Name, colour,
crystalline syslem
Considered
tz)
NiO
-12
Ni3Oa h1dr.
+3
+i
Ni Or lt"'"dr.
i2
2.r.r.
51 6.10
b. - ii1300
)110 150 (t)
270 (x)
rhomb.(r)
Nickelous oxide, grey, cub.
Dihydrated nickelo-Dickelic oxide
Ni304 .2H'O('z)
03 ltydr.
NiOII+
\io;
\io:
i3
Ni+++
Ni
2.
a. -
Ni++
substances
r. Two
li1dt.
-r'2.6j
Dissolved
2.
-0
-
Ni
solid substances
-112
NirO. . HrO,
nt
11 530
83
420
black('z)
(')
NiO,.2HrO,
black('z)
Dinickelite ion
Nickelite ion
46i (r)
Nickelic ion
Nickelate ion
o,
DrssoLvED SUBSTANCES
r^.(HNio'':-lu
'"o I N r++)
1.
-+ J t\rl
\i+-
/lr
Ni
o,
SUBSTANCES
9.
Ni
1 2 ->-t 2 6i
3.
-+zll' -+ze-
3NiO -r llrO:
Ni3Oa
2NiO -+ II:O=
Ni2O3
+2-:. + 3
4.
oft.
r II* -rrc
u
a. [1:
,.
0
0.
a Il,:
6. :
d. ljo:
'1.032 0
t).
0.876
0.0i91
0591
ltll
pII
for the oxides correspond to the iollowing values lor the hydroxides and hydrated oxides:
Ni(OH),:
Ni,O3.HrO:
168 960
cal,
332
CHAPTER
+ 2.67 >-+
5.
3 >n-
IV.
SECTION
12,3
lro:
I .30i-0.0J91 rrII
Do:
6.
irOs
IIl
:2
Ni
02 -t r-ll+ -t2e-
.432
0.0d91
pli
7.
+zH+
a.
log
(Ni++) :
12.18 2lH
(HNiOt): :-
12.41
-2 yH
r8.29 + pII
17.99 + pH
b.
8.
NiO -F
II,
O:
II NiO;
H+
.z. Iog
b.
c.
10.
t
Ni
Ni
-+1t
- \i--i-2IIr0: IINiO;-+3H+ -+ze-
0.2i0
0 618-0
It,,:
llo:-
+ 0.029i
Ios
(Ni+-)
0886 pH -+ 0.02951og (H Ni
O;)
-> -+ 2.67
11.
3Ni++ _FJILO: Ni304 _r8H+ r:c
12.
3II Ni Ot+ II+ : Nir04 -+2H2O -+2e
-r2 >-t3
13.
, Ni++ +IILO:
NizOo -+6H+ +2e
-+ 2->-+ i
14.
Ni++ r2H,O: Ni 02 +,1II- + 2 e-
3. reutLtgRrur.{
3.I.
Ilo: -
Eo
ESTABLISHMENT
oF THE
Ilo
1.753-0.lii3 pH
0.0591 los
0.02951o9 (Ni++)
593-0.1182
pH
(\i++)
DIAGRANIS
Using relations (1fi14) we have constructed, in Fig. r, a potential-pH equilibdum diagram for
the system nickel-water at 25'C.
From Fig. I we have derived Fig. 2, representing the theoretical conditions oI corrosion, immunity
and passivation o[ nickel at 25'C.
In Fig. 3, Fig. z has been reproduced, and Lhe experimental results of various investigators have
been added to it.
Figure 4, deduced from Fig. 3, shows the probable expedmental conditions of corrosion, immunity
333
NICKEL
3.2.
as
asmallzoneincommonwiththatofwater(FigI).ItiSdistinctlymorenoblethanilonwhichhasno
noble than cobalt'
zone of stability in common with that of water, and is slightly more
-z
t3
-1
14
15
?,7
E(V)
16
1,8
1,6
1,?
I
0,8
0,6
0,6
o,4
o,4
.',++
t\r
a,?
o,2
(oH)z
-o,?
- 0,4
-0,6
-0,8
-1
-1,2
-1,4
-1,4
-1,6
-1,6
-1,8
14
-1,8
15PHt6
11c I Polcntial pH cquilibrrLrm diagr'rm ior (hc systcm nrckcl $alcr' at 25'C
AccordingtothetheoreticaldiagramsFigs.Ianduwhichareverysimilartothecorresponding
d groms for "cobalt, the corrosion rlsistance ol nickel should depend as follows on the pH and the
or
. i.nce of oxidizing agents. for non-complexing solutions; it should be uncorrodible in neutral
oxidiztng
:lkaline solutions frJe 1iom oxidizing agents, slightly corrodible in acid solutions free from
.g.,rri, urO very corrodible in id & viry alkaline solutions containing oxidizing agents Neutral or
protection of
rlightly alkaline oxidizing solu ns should cover it with a layer of oxide. The cathodic
CHAPTER
394
IV.
SECTION i4.2
l.
Oidation
lzJ
oAg
Solid substances
.r.
b. -
AE2O
lrldr'.
+2
,As
r3
Dissolved substances + I
-1
\o+
Ago
Ag*,\so+
+3
2.
2.r. Two
J86
12726 (!)
'2
2G00
20800
'18 430
L90
- t;Li 100
53|,00
Agzog
',2
Ag' o
o.5
rr
NaD.
crvsrallin
,o(cal,
Nor
Considered
Sesquioxide,
, cub.
DISSoLVED SUBSTANCES
,1.
Ag.r
AS* +
-r e
A3+-r
: AgO+
AgO-
- L-,t 1
\-i + -+ l{r0:
S.
+-
''c-
(ASO2:_Cl.O,n*eplt
roC
(Ar)
rAcF+)
ll0:'1 980
Lo:
1 998
0 0:;' I PII -r 0
0205 1oS
{,\s0
1{*i
lto:j 288
*o relSr'Sffi
-F0 0i9l
rAsO.)
l"{GF-+)
substdnces
2.t.2. Linits of the donqins of relatiue predominance of the dissolved
:
{J2
pll 12.
Ag: /,\90I
Eo: r.980
,\r'
/,\s+
II,:
lh:
As+ /Aso
Aso-/As0r
r\s++/lS0rL
ll1:
1-998
1.288
2.016
0 0J!1 Pll
{'189
P}l
SUBSTANCES
oxides
Limits of the domains of relatiue stability oJ siluer and its
'(:. '
+ l -'. 12
i.
+-2 >+3
8.
('z)
2A9 + IllO:
+.
r}lr-'r 2a
tI,O
A92O3
r 2 H' + z r:-
pl.oH: pL"o
a lil
,..
12
I for
13)
huJ
Ag2O
-2
586 cal:,
395
SILVER
SUBSTANCE
9.
-r IIlO:
|\g-
10.
AgrO
-r-
11.
r.\
12.
O-r
As
t:1.
AgI
1t
16.
-+r>t3
17:
ftl.
-rrj.+il
l9
+ 2ll
H,0 :
-+ zH+
Ag, 03
2II'F
{o
-
,:-
Ito:
0.791)
E0:
2.920
ltt: l-712
rii : 0. 3ii /
+ 0.0591 log(,191 )
0. 1182 |lH -+ 0.059:l log ( Ag O- )
0.1182 t)H
0.0591tog(AS+)
0.05911og(AgO-)
0.0886 Pu
0.0995 pH
'l . (i70
l 0:
0.960
2r\g:' r3lls() :
tr,,:1.100-0
3,
3.r.
AEO
tii.
0.33-l)II
: ,r.gi-l)It
a. log(.{gO ):- 17.72 + l)l[
: - 12.10 -t pll
b.
log(,\s-"+) : - 3.iJ - 2PH
lI.I0-PH
log(,\ g O+ ) :
b.
IIjO:2,\[0-
-r HrO :
Ag2O +-zIl'
ESTABLTSHMENT
AE2O3
1.6II- r
2e
Iii
1773
l,H
-0.o}gl
log(Ag+.)
oF THE DIAGRAM
Using the equilibrium formulae established in paragraph 2, we have constructed Fig I' which
I,
represents the st;ble equilibria of the system silver-water, at 25"C. Figure z, deduced from Fig.
2_5"C.
In
at_
of
silvel,
represents the theoretical conditions of corrosion, immunity and passivation
nig.:wehaveusedequations(1'),(9)and(10)torepresenttheinfluenceofpHonthesolubilityof
AgrO
'- and AgOp are valid only in the absence oI substances with which silver can form soluble
ltrese diagiams
stable,
complexes or iisolubte salts. Silvei forms a large number of complexes, some of which are very
spalingly
salts
are
all
silver
e!. the ttriosulphuric and cyanide complexes of monovalent silver. Almost
so-luble; the niirate, perchlorate, fluoride, acetate and chlorate are soluble [2]'
3.2. srABtLITy AND coRRosloN oF
SILVER
of
silver is a very noble metal : its domain of stability covers a very lalge portion of the domain
stability oI water.
It ls found in the native state in nature, often mixed with other metals (Au, Hg, Sb, Cu, Pt 1n
pa
'
icular).
Silvei is perfectly stable in the presence of water and aqueous solutions of all pH's free from
(prooxidizing age;ts and complexing subitances; it is not attacked appreciably by dry or moist air
vided that the air is free from ozone, sulphuric acid, halogens and ammonia [8])'
In agreement with Figs. r and z, silver can be dissolved by acid oxidizing solutions to give coloulless
Ag* ionJlHNO., concenirated H2SO4, HCI in the presence oI oxidizing agents) In neutral or moderoxidize solutions
at"ely acid media, very powefful o*idiriog agents (such as ozone or the persulphates)
presence
of water and
the
in
unstable
which
are
AgrO3
and
AgO
of Ag+ to give ihe bl;ck oxides
lead to the
can
agents
oxidizing
these
media
very
acid
ln
of
ixygen
decoi.rpose it with the evolution
396
CHAPTER
IV,
SECTION
14.2
formation o[ black solutions of divalent silver, whose constitutjon is not known with certainty (Ag+
ions?, nitric or other complexes?)(a) [3]; these solutions, whose potential is around z V, are powerful
*
+*
oxidizing agents. As Noyes et rrl. have shown [3], they oxidize H2O2 to 02, Mn+ to MnOJ, Ce+
to Ce+ + + *, Tl+ to Tl+ + +, VO+ * to vor, Iot to Io; and NHi to N2 and oxides of nitrogen; the
dilution of these solutions leerds, together with an increase of pH, and according to reactions simtlar to
*
those represented by lines (2'), (3') and (5'), to the dispropofiionation of the divalent silver Ag*
i5
16
-t-t2,?
?
1,8
i,6
1,4
t,z
Agio"
1
0,8
0,6
0,4
0,?
0
-o,?
- o,4
-0,6
-0,8
-1,?
-1,4
-'1,6
-2 -l
o I ? 34
FIc I. Potentral pH
5 6 7I910
11 12 13
14
' l-1,8
15pHl6 '
into trivalent silver AgO* and monovalent silver Ag+, according to line (3'), with lhe separation of
basic substances containing Ag,,O..
Iu alkaline solutions, silver is generally stable; in the presence o[ oxidizing agents it covers itsell
with a film of brorvn AgrO, slightly soluble in caustic alkali solutions; silver is attacked by fused
hydroxides in the presence of oxygen.
(a) In nirric acid soiLrlion, Ag* - ions probably cxist jn the torm of complexcs. which would make AgrOr nro.e soluble than
shown by lines (19) and (17) of Fig I.
rs