NICKEL

l.

AND SUBSTANCES NOT

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.

Nickel, silvery white, f.c.cub.

Hydrated oxide or nickelous
hydroxide Ni(OH)r, green,

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

Monohydrated nickellc oxide

NirO. . HrO,

nt

11 530

83

420

black('z)

Dihydrated nickel peroxide

(')

NiO,.2HrO,

black('z)

Nickelous ion, green

?

Dinickelite ion
Nickelite ion

46i (r)

Nickelic ion
Nickelate ion

o,

REACTIoNS AND EQUILIBRIUM FoRMULAE(4)

DrssoLvED SUBSTANCES

Relatiue stability of the dissoloed substqnces

r^.(HNio'':-lu
'"o I N r++)

Nr-+ +2II:O: HNiO, +3IIr

1.

-+ J t\rl

2.1.2. Limits of the (lomains of relatit)e predominance of the dissolued suhstances

\i+-

2.2. Two soLID

/lr

Ni

pII :10. lil

o,

SUBSTANCES

Limits of the domains of telatiue stabilit)' of the soLid substances

9.

Ni

r H.rO: NiO + rtl" +2?-

1 2 ->-t 2 6i

3.

-+zll' -+ze-

3NiO -r llrO:

Ni3Oa

2NiO -+ II:O=

Ni2O3

+2-:. + 3

4.

(r) These values

oft.

r II* -rrc
u

a. [1:

,.

0
0.

lt0-0 0i1]l pII

l16 0.059t1)ll

a Il,:
6. :

0 897-{) 0i!1 plt

d. ljo:

'1.032 0

t).

0.876

0.0i91
0591

ltll
pII

1.090 0 0d91 III

for the oxides correspond to the iollowing values lor the hydroxides and hydrated oxides:

Ni(OH),:

108 300 cal.,

Ni,O3.HrO:

168 960

cal,

NiO, 2HrO: - 164 800 cal

Ni3Oa 2HrO: -283 530 cal..
(')All these values have been justined elsewhere [1].
is
(a) ln reactions iD which Nio takes part, the letter 4 refers to Ni(oH)r_whose free enthalpy of formation
the letier b refers to anhydrous NiO whoie free enthalpy of formation is - 51 300 cal'

108 300 cal.;

332

CHAPTER

+ 2.67 >-+

5.

3 >n-

IV.

SECTION

12,3

zNi3Oa-r IIrO:3 NizOs +zH+ +ze-

lro:

I .30i-0.0J91 rrII

Do:

6.

irOs

2.3. oNr solro

IIl

:2

Ni

02 -t r-ll+ -t2e-

.432

0.0d91

pli

suBSTANCE AND oNE DtssoLVED suBsrANCE

Solubility of the solid substances

7.

Ni++ + HrO: NiO

+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:-

1.977- 0 236/r pH-0.08861o9(Ni++)

0.718-+0 029i pli-0.0886 1og (HNi O;)

+ 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++)

DTACRAM AND ITs INTERPRETATToN

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

and passivation of nickel in solutions not containing chloride.

Using relations (1'), (7) and (8) we have represented, in Fig. 5, the influence of pH on the solubility
of nickelous hydroxide N(OH)r.
Figure 6 shows the equilibrium conditions of the principal reactions liable to take piace at the
iron and nickel electrodes of iron-nickel accumulators, during their charging and discharging.
It should be remembered that most of these diagrams are valid only in the absence of substances
with which nickel can form soluble complexes or insoluble salts.
Charlot [2] mentions the existence of the following complexes: hydrochloric and sulphuric (very
unstable), ammine (fairly unstable), oxalic, thiocyanide, metaphosphoric, pyrophosphodc and cyanide.
There is a large number oI sparingly soluble compounds : the least soluble ones are the ferri- and
lerrocyanides, and in particular the black sulphide NiS and the red nickel dimethylglyoxime.

333

NICKEL

3.2.

STABILITY AN-D coRRosIoN oF NICKEL

Nickel can be considered to be a slightly noble metal,

as

ils domain of thertnodynamic stability has

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

suBsrANCEs CoNSIDERED AND SUBSTANCE NOT CONSIDERED

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

Silver, greY, cub.

Sub-oxide

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

Argentous oxide, brown black, cub.

HYdrated oxide or
hYdroxide AgOH, white
Argentic oxide AgrOr, grey black, cub

Sesquioxide,

, cub.

Argeotous ion, colourless

Argentite ion, ?
Argentic ion, ?
Argentyl iotr, ?

REACTIoNS AND EQUILIBRIUM FORMULAE (3)

DISSoLVED SUBSTANCES

2.tt. Relatiue stability oI the dissolaed substances

7.:)_r
Ag- + H:O: AgO- -2Ht.
at 2-z
9.
+-r >-r i
3.

,1.

Ag.r
AS* +

-r e

A3+-r

lIzO: r\go- +2H+-r 2-

: AgO+

AgO-

- L-,t 1
\-i + -+ l{r0:
S.

+-

''c-

.\uoo l-2H++ r'

(ASO2:_Cl.O,n*eplt

roC

(Ar)

rAcF+)

-+0 050t lng:--r-'

ll0:'1 980
Lo:

1 998

0 0:;' I PII -r 0

0205 1oS

{,\s0
1{*i

lto:j 288

*o relSr'Sffi

li,r:2 0t6-0 lltt:1'll

-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

2.2. Two soLID

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

Ag2O-+ II,O :2AgO '+'2H1 a 2c

zAEO r

tI,O

A92O3

r 2 H' + z r:-

{ 173-0 0iiC1 pII

.505
- 0 059' pH
'1

a ljo 3C8-0 0591 pl[

'i1 066 0'0591 pll
b)!': { 569 -0 0ii91 pH

- Ago- +H+ From thrs we can deduce

2po^'o' - A'o= +l2726cal
-(121x 1,363) = -2l9E2cal and rl!'ohvd' =
offormation is

Charlot [2] gives pK

pl.oH: pL"o

a lil
,..

12

I for

the reaction AgOH

Ag2O, whose free enthalpy

tn reactions in whrch AgrO rakes part, letter d tcfers to anhydrous
or rormation is -21 e82cat'
enthalpv
free
*hose
&oil,
;;H;:';;;.";;;;;,tr;'

13)

huJ

Ag2O

-2

586 cal:,

395

SILVER

2.3. oNE soLID suBsrANcE AND oNE DISSoLVED

SUBSTANCE

Solubility of siluer and its oxides

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
-

,:-

AgO +,2Ht-t e-'

-t cASO

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

0.0295 log( AgO-1

2,\g-" + 3HlL): Ag2O3r0II-rlc: ,\gO -r-. H, O : Ag2os-t 2H+ a- 4c-

'l . (i70

l 0:

0.960

2r\g:' r3lls() :

tr,,:1.100-0

3,

3.r.

AEO

H,O: .\cO - +zH-t

ljrO:
:

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 :

rl. los(As ts) :

Ag2O +-zIl'

ESTABLTSHMENT

AE2O3

1.6II- r

2e

Iii

1773

l,H

0.029i log( A8-+

-0.o}gl

log(Ag+.)

EQUILIBRIUM DIAGRAM AND ITS INTERPRETATION

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 '

equilibrium diagram lbr thc system sih'er $ater, at 25'C

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