CHAPTER 21

INHIBITION OF THE CORROSION OF

COPPER IN SODIUM HYDROXIDE
 '4 f |

CHAPTER V

INHIBITION OF THE CORROSION OF COPPER IN

SODIUMHYDROXIDE SOLUTIONS

Few metals are completely proof against attack by alkali!.

Silver, nickel and certain stainless steels are the best.
Alkalies attack vigorously those metals, the hydroxides
of which are amphoteric, e.g. metals such as Aluminium
and Zinc. The corrosion of these two metals in alkalies
have been the most studied and also various inhibitors
have been mentioned. In recent years inhibitors are
being used to protect nonferrous metals and their alloys;
previously they were only used to slow down the corrosion
of ferrous metals.

A. CORROSION OF COPPER IN SODIUM

HYDROXIDE SOLUTIONS
Copper is slowly corroded by alkali but the action is
appreciable. Fuller and his associates1 studied the
corrosion of copper in 1.ON sodium hydroxide under the
condition of total and alternate immersion and also by
spraying of alkali. The corrosion rate reported by them
is 14 m.d.d. for quiet immersion, and 20 m.d.d. for air
agitated total immersion. Lower rates of corrosion of
copper have been reported by some workers3 and higher
rates by others3. Payen4 observed that copper is oxidized
in a dilute solution of potassium hydroxide and the

action is more particularly marked where the metal is

in contact with air and water at the same time. When

copper is sprayed with a concentrated solution of alkali

hydroxide, it is coloured brownish black in a few hours

by exposure to air, the action being slower in dilute

solution.

Lucion6 states that cupric hydroxide is soluble in alkali

lye at 15°C, Fischer6 states that the solubility of

cupric hydroxide in soda lye is less the more dilute the

lye. Muller7 states that when cupric oxide or hydroxide

is shaken with concentrated solution of sodiumhydroxide

the amount dissolved depends on the concentration of

alkali.

The solubility of cupric hydroxide in alkali lye is aug­

mented by the presence of many organic substances^.

The action of alkalies and alkaline liquids on the corro­

sion of copper and its alloys has not received sufficient

attention. Desai et.al9 studied the influence of anions

on the corrosion of brass at different pH values. In

solution containing phosphate or acetate ions corrosion

of brass decreases with increase in pH and becomes

negligible at pH values higher than 6.1. In solutions

containing citrate or malate ions, corrosion decreases

with increase in pH, is minimum at pH 4.85 and then

decreases again. This is due to the formation of sodiun

citrate or malate, both of which are highly corrosive,

»
On the other hand with phosphate and acetate ions corro*

sion of brass is practically negligible in the alkaline

range. Those anions which form stable films in alkaline

solutions inhibit corrosion. Thus it was found that the

protective influence of phosphate ions in alkaline range

is not seen in the presence of citrate ions due probably

to the tendency of the latter for complex formation.

Perry1® studied the effect of sodium hydroxide on the

corrosion of copper at high temperature. Shatalov1?

{

studied the corrosion behaviour and stationary potentials

of copper with varying hydrogen ion concentration.

Barannik12 studied the corrosion of copper in sodiumhydro—

xide solutions. The rate of corrosion in aqueous sodium

hydroxide solution increases from 0 to 0,045 gm/m2/hour as

sodium hydroxide concentration is increased from 0 to 0.5

gm equivalent/liter and then decreases gradually.

B. INHIBITION OF THE CORROSION OF

COPPER IN ALKALINE SOLUTIONS

Checkley and Healings 13 used potassium dichromate as an

inhibitor for the corrosion of copper in alkaline solutions,

Lacan et.al.l4»' studied potassium dihydrogen phosphate,

stannous chloride, napthpnic acid, oleic acid and cobalt

linolate as inhibitors for the corrosion of copper in

sodium hydroxide solutions and observed that of all the

compounds studied, the last compound was most efficient,

Desai and Rana^® studied about 30 substances as inhibi~

tors for the corrosion of copper in sodium hydroxide

solutions. Nearly complete protection ( >99%) is

afforded by resorcinol, oinapthol, glucose, furfuraldehyde,

and hydrazine sulfate. The following substances retarded

the corrosion to an extent of 90% or more! m-amino

phenol, p-aminophenol, cyclohexanone, 8 hydroxyquinoline,

quinalazarin, hydroquinone, sodium diethyl dithiocarbamate,

sodium rhodizoante, gallocyanine, phlorogTucinol and

acrifld,v;ine. It was observed that the performance of

catechol, m— cresol, pyrogallol, tannin, ip napthol,

p-nitroptienol, salieylaldehyde, 2, 4 pentanedione, acetone,

cupferroa, cupron, thiourea, dithioxamide and sodium

Op
chromotr^e’vas fairly satisfactory. It was observed that

in most of the cases, the protection afforded was due to

the formation of a film over surface of metal specimen.

C. LITERATURE SURVEY OF SUBSTANCES'STUDIED

BY US AS CORROSION INHIBITORS FOR OTHER
METALS AND ALLOYS

Glucose has been used as an inhibitor of the corrosion of

aluminium in alkali*5 of copper in nitric acid1^, aqueous

* i

ammonia18 '§>3 ^ SlV and in sodium hydroxide solutions15,

19 .
during the manufacture of furfural-*-

The uses of furfuraldehyde as corrosion inhibitor have been

reported in Chapter III. ,

 4 SF

Acetone has been patented as a constituent of a corrosion

Inhibiting composition2®, it has also been used to

retard the corrosion of aluminium in carbontetra-

chloride2-*-, the corrosion of iron in hydrochloric acid

and.the corrosion of copper in sodium hydroxide solu­

tions1® e

2,4 pentanedione has been investigated as an inhibitor

of corrosion of iron, zinc and cadmium in >hydrochloric

acid23, and the corrosion of aluminium24 and copper in

sodium hydroxide solutions15. ,

Cyclohexanone retards the corrosion of steel in sulphuric

o „ 25
acid at 70 - 100 C and the corrosion of copper in

sodium hydroxide solutions15 and potassium persulphate

solutions^6 the corrosion of 63/37 brass in alkali27.

Phenol has been used to retard the corrosion of iron in

sulphuric acid28, and the corrosion of aluminium in

hydrochloric acid 29 .

Catechol has been used to retard metallic corrosion by

alcoholic motor fuels30, by lubricating oils31 for the

oo
corrosion of aluminium in hydrochloric acid and xn

alkali32 the corrosion of carbon steel in carbon tetra­

chloride33 and in alkali34 the corrosion of lead in soft

water 35 and the corrosion of copper in alkali 15 .

Resorcinol has been used to inhibit the corrosion by lubricating

 4 ? s?

oils, the corrosion of aluminium in hydrochloric acid29

and in alkali32, for the corrosion of lead in soft water35*36

in distilled water3 7 , and the corrosion of copper in

alkali*.;?-.-

Hydroquinone has been used to retard the corrosion of

aluminium in hydrochloric acid29, the corrosion of lead in

soft water33’3®, and in distilled water37, and the corrosion

of copper in alkali15.

Pyrogallol has been suggested as an inhibitor for the

corrosion of iron in sea water3 8 , the corrosion of ferrous

metals by light hydrocarbons39, and the corrosion of copper

in sodium hydroxide solutions15. It is not a very satisfac­

tory inhibitor for the corrosion of Aluminium in hydro­

chloric acid29.

Phloroglucinol is an excellent inhibitor for the corrosion

of copper in alkali15.

Salicyls^lehyde retards the corrosion of iron in acidic

solutions49 and the corrosion of copper in sodium hydroxide

solutions15, and in potassium persulphate solutions26.

m-Cresol has been used to protect buried metal objects41,

and the corrosion of copper in alkali15. (

o—aminophenol and m-aminopheno1 have been used as corrosion

inhibitor*for aluminium in alkaline medium**.

p-amino phenol has been reported as a volatile corrosion

inhibitor43*44, and as an inhibitor for the corrosion of

aluminium in alkaline media42, the corrosion of titanium

in sulphuric acid4 5 *4 6 *47 and in HCl47, the corrosion of

copper in alkali15,

ike,
p-nitro phenol has been used to prevent corrosion of steel

tank in sea water48, the corrosion of titanium in sulphu­

ric46* 47> 49 and hydrochloric acids47* 4S, the corrosion

of steel in sulphuric and in hydrochloric acids49, the

corrosion of copper in alkali15, and as a volatile corrosion

inhibitor50,

cL —napthol has been used to prevent corrosion by lubricants5

the corrosion of mild steel by carbontetrachloride~water

vapour mixture52, the corrosion of Aluminium in hydrochloric

acid29, the corrosion of copper in alkaline media 15 and as

a volatile corrosion inhibitor50.

-napthol inhibits the corrosion of lead in nitric acid ,53

the corrosion of copper in alkali 15 and has been reported

as a vapour phase inhibitor54 ’ 50’ 55’ 55, and a rust

preventive57. It is not a very satisfactory inhibitor for

corrosion of Aluminium in hydrochloric acid29.

P
Sodium Ehodizonate, quinalizarin and sodium chromot rc^at e ,

have been studied as inhibitors for the corrosion of copper

in alkaline media15. Sodium chromoiropt^ate retards corro-

I

sion of brass in alkali27.

8-quinolinol prevents the corrosion of cast iron during

the manufacture of furfural58, and inhibits the corrosion

of brass in alkali2?, the corrosion of metals by fuming

nitric acid®®. It also inhibits the corrosion of aluminium

in alkali6^ and in carbon tetrachloride®^ and copper in

alkali1®. Its adsorption on mercury has been evaluated62.

Sodium diethyldithioCcarbamate has been used as a corrosion

inhibitor for iron®®.'|^ It has been studied as an

inhibitor for the corrosion of carbon steel in dilute

sulphuric acid64. It affords excellent protection to

copper and brass in sodium hydroxide solutions1®.

The uses of mereaptoacetic acid and thiourea as inhibitors

have been reported in Chapter II.

Dithioxamide has been studied to prevent the corrosion of

copper1® and brass in alkaline media27.

Acriflavine has been studied as an inhibitor for the

corrosion of steel in sulphuric acid6®* 66 fjl?) and

for copper in alkali1®.

Cupron, Cupferron, and gallocyanine have been studied to

retard the corrosion of copper in sodium hydroxide

solutions15. The uses of tannin as corrosion inhibitor

are given in Chapter III.

RESULTS AND DISCUSSION

In 0.5N sodium hydroxide, copper is corroded to a greater

extent than that in 0.2N and l.oN solutions.

Phenol: C TABLE V ~1 , V-1 )

At 2.17 ml/l concentration, phenol is more effective in

0.-2N and l.oN sodium hydroxide solutions as compared to

that in 0.5N sodium hydroxide which, however, in the

presence of 4.35 ml/l of phenol, the corrosion of copper in

all the three concentrations of alkali is retarded to more

than 90%. The corrosion of copper in 0,2N sodium

hydroxide solution is practically completely eliminated in

the presence of 17.$0 ml/l phenol whereas the corresponding

inhibition in 0.5N and l.oN sodium hydroxide solutions is

about 94%.

Catechol! C TABLE V-i , F f G V 'l )

In all the three concentrations of alkali studied, the

corrosion of copper is retarded to a greater extent at 0.1%

concentration of catechol. At this concentration of the

inhibitor, retardation of the corrosion is maximum in 0.5N

sodium hydroxide solution followed by 1.0N and 0.2N sodium

hydroxide solution. With further increase in the

concentration of catechol percentage retardation decreases

and at 1.0% concentration of catechol, the corrosion of

copper in 0.2N sodium hydroxide solution becomes almost

equal to that in uninhibited solution. In l.oN sodium-

hydroxide solution percentage inhibition falls off to

19.5% at 1% concentration of the inhibitor. The retarda­

tion in percentage inhibition in 0.5N sodium hydroxide

solution is less as compared to that in 0.2N and 1.0N

sodium hydroxide solutions.

At 0.1% and 0.2% inhibitor concentrations reddish brown

films are formed over the metal specimens. The corrosion

of copper in 0.2N, 0.5N and 1.0N solutions can be inhibited

to an extent of 73%, 89% and 83% respectively at 0.1%

concentration of catechol.

Resorcinols £ T/SJ91F , F1& V~J.)

Resorcinol appears to be a very good inhibitor for copper

in sodium hydroxide solutions. Thus at 0.05% concentration

of the inhibitor, the percentage inhibition is between

90—95%* The inhibitor efficiency is dependent on the OH

concentration is very well reflected by results obtained at

0.01% of resorcinol. At this concentration of the

inhibitor the percentage efficiency in 0.2N, 0.5N and 1.0N

sodium hydroxide solutions are respectively 37%, 53% and

91,8%. Thus at higher alkali concentrations, resorcinol

functions as an efficient inhibitor even at lower concentra­

tion of the inhibitor. However, beyond 0.01% concentration

of the inhibitor the effect of alkali concentration is not

perceptible and at 0.05% concentration of the inhibitor the

percentage inhibition at the three concentrations of alkali

is between 90 to 95%. At 1% concentration of resorcinol

the corrosion of copper in 0.2N, 0.5N and 1.0N sodium

hydroxide solutions is almost practically inhibited.

Thin reddish yellow films are formed over the metal

specimens whenever the inhibition is 90% or above and

which turns violet on treatment with sulphuric acid.

Hydroquinone* C T A B L 'E V- 1 P F16 V •1 A ) ,

The retardation of the corrosion of copper in presence of

hydroquinone is maximum in 1.ON sodium hydroxide solution

and lowest in 0.2N sodium hydroxide solution? however,

when the concentration of hydroquinone is increased to

1.0% the corrosion of copper in 0.2N, 0.5N and 1.0N

sodium hydroxide solutions is retarded to an extent of

96%, 94% and 78% respectively. Thus, with 1.0%

hydroquinone the corrosion of copper is retarded to a

greater extent in 0.2N and 0.5N as compared to that in

1.0N sodium hydroxide solution. The protective power of

hydroquinone falls off in 1.0N sodium hydroxide solution

from 85 to 78% when the concentration of the hydroquinone

is increased from 0.2 to 1.0%.

Thin reddish brown films- are formed over the metal speci­

mens at concentrations of the inhibitor corresponding to

appreciable inhibition
 Pyrogalloi: C .T A B L E V l , FIG. V I A >

At low concentration, pyrogalloi is more effective in 0.2N

sodium hydroxide solution. At 0.01% concentration of

pyrogalloi inhibition of corrosion in 0.2N sodium hydroxide

solution is about three times greater than that in 0.5N

sodium hydroxide solution. Results obtained in 0.2N sodium

hydroxide•solution and those obtained in 0.5N and 1.0N

sodium hydroxide solutions are quite different. Thus in

0.2N sodium hydroxide solution, with increase in the

/
concentration of the inhibitor,corrosion decreases and
J
-maximum inhibition (82.4%) is reached at 1% concentration

of the inhibitor whereas in 0.5N and 1.0N sodium hydroxide

solutions, maximum inhibition is reached at intermediate

concentration of the inhibitor and thereafter with further

increase in the concentration of the inhibitor the protec-

O

tive power of the inhibitor falls off. Thus at 0.2%.

concentration of the inhibitor retardation of the corrosion

of copper in 0.5N and 1.0N sodium hydroxide solutions is to

the extent of 80 to 83 per cent and with 1.0% concentration

of the inhibitor retardation of corrosion of copper in O.oN

sodium hydroxide is 36.5% and in 1.0N sodium hydroxide it

is 30%.

The corrosion of copper in 0.2N, 0.5N and 1.0N sodium

hydroxide solutions can be inhibited respectively to an

extent of 82% (inhibitor concentration 1.0%), 77% (inhibitor

concentration 1%) and 82% (inhibitor concentration 0.2%) by

 42B

pyrogallol. When the inhibition is above 70% metal speci­

mens were found to be covered with thin brown films.

Phloroglucinol* ^ Tfi'&LB V-?LA f F l & V II)

When the concent ration of phloroglucino1 is 0,001%, the

inhibition is greatest in the case of 0.2N alkali (41.2%)

followed by 1.0N (19.0%) whereas in 0.5N alkali there is an

acceleration of corrosion to the extent of 21.5%. Thus in

contrast to resorcinol, phloroglucinol is more effective in

dilute alkali at low concentrations. At 0.2% concentration

of phloroglucinol^ the corrosion of copper in 0.2N, 0.5N and

1.0N sodium hydroxide solutions is retarded to the extent of

95%, 95%, and 89% respectively.

Between 82 to 95% inhibit ion^ metal specimens were covered

with yellow film.

o-Aminophenol • C TABLE * V rL®.)

The results obtained with o“amlnophenol are interesting.

The efficiency of o-aminophenol increases with the concen­

tration of alkali. In the presence of 0.01I& o-aminophenol,

the corrosion of copper in 0.2N, 0.5N and 1.0N sodium

hydroxide solutions is retarded respectively to an extent of

9.3%, 68.4%, and 81.1%. Beyond 0.OlKfl. concent ration of

o-aminophenol, its efficiency decreases in 0.5N and 1.0N

and in 0.2N sodium hydroxide solution, the corrosion of

copper is accelerated.
 . ../■ TARlF V-? j5,FiS
m-aminophenol and p-amxnophenol* I 1 fit>LC v ■*- J
V 1 B1
At 0.01% concentration of m-aminophenol, the corrosion

of copper is retarded to a greater extent in 1.0N and 0.2N

sodium hydroxide solutions. This type of behaviour

persists upto 0,05% concentration of m-aminophenol.

Thereafter there is also appreciable inhibition of

corrosion in 0.5N sodium hydroxide solution and at 0.5%

fcka-
concentration of the inhibitor, corrosion of copper in
h
0.5N and 1.0N sodium hydroxide solutions is retarded to

an extent of 94% and 91% respectively, whereas in the

case of 0.2N sodium hydroxide solution, it is approximately

87%. In the case of 0.2N and 1.0N sodium hydroxide

solutions when the concentration of the inhibitor is

increased from 0.05% to 0.1% the increase in the

percentage protection is 8% and 6% respectively whereas in

the case of 0.5N sodium hydroxide solution there is a

sudden increase in inhibition by about 50% when the

inhibitor concentration is increased from 0.05 to 0.1%.

In the case of p-aminopheno1, inhibitor power increases

with the increase in alkaline consent ration at all concen­

trations of the inhibitor. If we compare the results

obtained with m-aminophenol (0.1%) and p-aminophenol (0.1%)

it can be seen that in 0.5N and 1.0N sodium hydroxide

solutions p-aminophenol is more effective than m—aminophenol

A
At a concentration of 0.1% p-aminophenol the corrosion of

copper in 0.2N, 0.5N and 1.0N sodium hydroxide solutions is

 retarded to an extent of 7 8 , 5 , 90 and 90% respectively.

Aminophenols are known to react with copper to form

inner complex salts and inhibition thus will depend upon

the stability of the complex, pH and the effect of the

excess inhibitor on the solubility of the complex formed

over the metal surface. With m and p-aminophenols,

' between 70 to 94% inhibit ion^ thin brown films are formed

v ' over the metal specimens.

r
If we compare the results obtained inpaminophenol and
*A

p-nitrophenol, at a concentration of 0.01% it will be

evident that with p-nitrophenol there is no inhibition of

corrosion in 0.5N and l.oN sodium hydroxide solutions.

At 0.1%, concentration of p-nitrophenol, the percentage

inhibition in 0.2N, O.sN and 1.0N sodium hydroxide solutions

is reduced by about 42%, 76% and 68% than that obtained at

corresponding concentration of p—aminophenol. With

p-nitrophenol^ inhibition is comparatively more in 0.2N

sodium hydroxide solution.

At 0.5% concentration of p-nitrophenol^ the corrosion of

copper in 0.2N, 0.5N and 1.0N sodium hydroxide solutions

is reduced to an extent of about 56%, 21% and 34% respectively.

t
„ Brown films are formed over the metal specimens.

m-Cresoi: C TABLE v-jLA , FIG V I S )

Though not as efficient as resorcinol, n-'cresol behaves

as resorcinol in the sense that at low concentration^

retardation of the corrosion of copper is maximum in

l.ON sodium hydroxide solution; When the concentration

of m-cresol is 2.17 ml/l, the corrosion is retarded to

an extent of 43% in the case of l.ON sodium hydroxide,

and about 20% in 0.5N and 0.2N sodium hydroxide solution.

However when the concentration of the inhibitor is

increased to 17.4 ml/l, the effect of alkali concentration

is not felt and the corrosion of copper is retarded

practically equally (73 to 75%).

Upto 8.70 ml/l concentration of the inhibitory black films

are formed over metal specimens which turns violet on

treatment with sulphuric acid. At 17.4 ml/l concentra­

tion of the inhibitor reddish violet films are formed

/

over metal surfaces.

Salicylaldehydes (.ThbLE. - V-1B> FIS.'V 1C)

Salicylaldehyde can be considered to be an effective

inhibitor only in 0.2N sodium hydroxide solution, with

26.1 ml/l concentration of salicylaldehyde^the corrosion

of copper in 0.2N, 0.5N and l.ON sodium hydroxide solutions

is retarded approximately to an extent of 88%, 48% and

31% respectively. Thus, at this concentration of the

inhibitory the protective power decreases with the increase

in the concentration of alkali. In this case also the

inhibitor appears to be due to the formation of complex

product over the metal surface and the difference in the

behaviour of salicylaldehyde in different concentrations

of sodium hydroxide solutions appears to be due to changes

in the stability of the complex. The complex appears to

be more stable and insoluble in 0.2N sodium hydroxide

solution and as a result greater protection in 0.2N sodium

hydroxide solution.

Greenish yellow film was formed over the metal surface in

0.2N sodium hydroxide at a concentration of 26.1 ml/l of

the inhibitor.

J ® t t /srle- V-1 B « FIG.-V-1C3

eL —n apt hoi and f! '-napthol J (.77b y

At 0.01% concentration of j^-napthol^ the retardation of the

corrosion of copper is more in 0.2N sodium hydroxide

solution as compared to 0.5N and 1.0N sodium hydroxide

solutions. However, at 0.1% of the inhibitor concentration

the corrosion is retarded to.greater extent in 0.5N and

A

„1.0N sodium hydroxide solutions as compared to that in

0.2N sodium hydroxide solution. At 0.5% concentration of

«|£g;
the inhibitor percent^, retardation of the corrosion of copper

in 0.2N, 0.5N, and 1.0N sodium hydroxide solutions is

practically identical (81 to 84%). 'aC -napthol and

p -napthol are known to give characteristic colourations

with cupric ions. Copper reacts with ^-napthol to give

a blue violet colouration and with ^ —napthol it gives

colour varying from yellow to blue.

Upto 0.2% concentration of f -napthol, the % retardation

of the corrosion increases with the concentration of the

alkali If we compare the results obtained at 0.05%

0,05^ concentration of ^-iiapthol and ^-napthol, it
will be evident that with JL,-napthol, the retardation
of corrosion is maximum in 0.2N sodium hydroxide
gj 'M**'
solution whereas withp^ -napthol^retardation of corrosion
l

is maximum in 1.0N sodium hydroxide solution. At 0.5%

concentration of Ji,-napthol}there is practically no
difference in behaviour with concentration of alkali
whereas in the case of ^ -napthol retardation of the
corrosion of copper decreases with the concentration of
alkali.

With oC —napthol the corrosion of copper is retarded to

-7

an extent of 81 to 84% (0.5% concentration of inhibitor)

whereas the corrosion of copper in 0.2N, 0.5N and 1.0N
sodium hydroxide solutions is reduced to an extent of
97%, 89%, and 84% by the addition of 0.5% of -napthol.
At 2% concentration of jj® —napthol there is practically
100% inhibition.

In the case of -napthol when the inhibition is between

70 to 84% thin yellowish brown films are formed over the
metal surfaces. With jp -napthol thin yellowish films
are formed over metal specimens^ whenever there is
appreciable inhibition (70 to 92%)^ which turns blue when
treated with sulphuric acid.

8 quinolinol* ( TA&LE v - i c , n e 13)_)

At low concentration of the inhibitor (0.01%) protection
 of copper increases with increasing concentration of

alkali!. In 0.2N alkali at 0,01% concentration of the

inhibitor there is acceleration of corrosion to the

extent of about 18%, At this concentration, the product

deposited on the metal surface was thick, fluffy and not

strongly adherent. At 0.05% concentration of the

inhibitor^ the corrosion of copper in 0.2N, 0.5N and 1.0N

sodium hydroxide solutions is retarded to an extent of

81%, 84% and 43.5% respectively. Thus, at this

concentration, the product deposited over the copper

surface in 0.2N and 0.5N sodium hydroxide solutions is

protective to a greater extent than' that produced over the

copper surface in 1.0N sodium hydroxide solution. In

general it can be said that 8~hydroxyquinoline affords

greater protection to copper in 0.5N sodium hydroxide

solution. This may be attributed to the favourable condi­

tion for the formation of a film of product of comparatively

more protective nature.

;When the concentration of 8“hydroxyquinoline is G.5%^the

corrosion of copper in 0.2N, 0.5N and 1.0N sodium hydroxide

solutions is retarded to an extent of about 91%, 93% and 88%

respectively. When the inhibition is between 80 to 93% the

metal specimens were covered with thin yellow brown film.

Cupferron* C TABLE V 1 F , FIS V IX)

ik*.
In 0.2N sodium hydroxide solution maximum inhibition (46%)

is obtained at 0.01% concentration of the inhibitor and with

 further increase in the concentration of the inhibitor
>
protective power of cupferron falls off and at 0.5% con­

centration of the inhibitor there is an acceleration of

corrosion to an extent of about 32%. These results

indicate that it is quite likely that in the presence of

the excess reagent^ solubility of the complex product

formed over the metal surface is increased and where the?e

is acceleration of corrosion^it can be concluded that

soluble complex is formed.

In 0.5N sodium hydroxide solution^ inhibitory effect is

maximum (about 38%) between 0.05% and 0.5%. In 0.5N

alkali there is no acceleration of corrosion at 0.5%

concentration of the inhibitor as that met with in 0.2N

alkali.

Thus the effect of alkali concentration on the solubility

of the complex is clearly seen. In 1.0N sodium hydroxide

solution at 0.001% concentration of the inhibitor^ the

corrosion of copper is retarded to an extent of about 52%,

'however, betxveen 0.01% and 0.2% of the inhibitor concent ra-

/tion^protective power falls off which again reaches

approximately to the same value as that obtained at 0.001%

concentration of the inhibitor.

*

The corrosion of copper in 0.2N, 0.5N and 1.0N sodium

hydroxide solutions is retarded to an extent of about 46%

(0.01% concentration ofinhibitor), 38% (0.5% concentration

 of inhibitor) and 52% (0,001% concentration of inhibitor}

respectively. Black films are formed over the metal

specimens.

Cupferron reacts with copper to form inner complex which

can be represented by the formula

-W - « o

0$

The gray-blue precipitate of cu-cupferron is easily co­

agulated and feebly decomposed by IN potassium hydroxide

at 18° C68. The fact that metal specimens are covered

with black films, confirms that the inhibitor action of

cupferron is due to its chelating action.

Cupron: ( T A B L E V I F , F IG V II)

At 0.001% concentration of cupron^there is practically

no' inhibition of corrosion of copper in 0.5N and 1.0N

sodium hydroxide solutions, whereas in 0.2N sodium hydro-

fcke
xide solution, corrosion is retarded to an extent of 28%.
m
Tk-Corrosion is retarded to a maximum at 0,05% concentration

of the inhibitor in all the three concentrations of

alkali. At this concentration, the corrosion of copper ia

retarded practically to the same extent in 0.2N and 0.5N

sodium hydroxide solutions. Thus the corrosion of copper

 4 f] 2

in 0.2N, 0.5N and l.ON sodium hydroxide solutions is

retarded at 0,05% concentration of the inhibitor to an

extent of 82%, 84% and 54% respectively. In 1.0N

sodium hydroxide solution, the lower protection may be

due to the influence of high alkali concentration. The

complex product formed over the metal surface must be

dissolved to a greater extent in 1.0N sodium hydroxide

solution. When the concentration of the inhibitor is

increased beyond 0.05%^the protective power of the

inhibitor falls off in all the three concentrations of

alkali. As the inhibitor concentration is increased from

0.05% to 0.2%jit is observed that in 1.0N, 0.5N and 0.2N

sodium hydroxide solutions the protective power of the

inhibitor decreases by 36%, 17% and 60% respectively. Thus

the adverse effect of the excess of inhibitor is predominant

in 0.2N sodium hydroxide solution. It is likely that the

solubility of the product deposited over the metal surface

is increased to a greater extent in the presence of the

excess reagent in 0.2N and 1.0N sodium hydroxide solutions

than that in 0.5N sodium hydroxide solution.

The corrosion of copper in 0.2N, 0',5N and 1.0N sodium

hydroxide solutions is retarded to an extent of about 82%,

84%, and 54% respectively by the addition, of 0.05% of

cupron. Between 53% to 84% inhibition^ greenish yellow

films are formed over the metal specimens!.

According to Feigl6 9 , the green insoluble copper salt of

We have observed that when cupron effectively retards

the corrosion of copper in sodium hydroxide solution,

the metal surfaces are covered with green films.

Sodium diethyl dithiocarbamate S ( T A B L E V 1 £ } Fl& V 1 H )

Thlf chemical appears to be unique in its protective action

on copper. It functions at low concentration in 0.2N

and 0.5N sodium hydroxide solutions. A strong,

extremely adherent, highly insoluble bond is formed on

the surface of the metal. Inhibition of the corrosion

CL
of metals through the formation of^film of complex product

over the metal surface in general can be looked upon as

anodic inhibitory. One characteristic often found with

i,

anodic inhibitor is the increased corrosion at concentration

below the optimum range of concentration. This type of

behaviour is also met with sodium diethyl dithiocarbamate.

In 0.2N sodium hydroxide solution at 0.001% and 0.002%

concentration of the inhibitor^there is an acceleration

of corrosion. As suggested by Evans16 if the control is

predominently cathodic thjBn small amounts of inhibitor

by allowing a greater cathodic area may increase the

corrosion rate. In the case of 0.2N and 0.5N sodium

hydroxide solutions^ the addition of 0.01% o.f the inhibitor

 '4 fi 4

the corrosion of copper is retarded to an extent of 95

to 98% respectively. However, in 1.0N sodium hydroxide

solution the protection is only about 27%. It appears

that complex dissolves to a much greater extent in 1.0N

sodium hydroxide^ solution, at this concentration of th?s

inhibitor. When the concentration of the inhibitor in

1.0N sodium hydroxide solution is increased from 0.01% to

0.05%,the corrosion is retarded to an extent of 95%. At

A*

about 0.2% of the inhibitor3 the corrosion is practically

inhibited in all the three concentrations of alkali. In

0.&N sodium hydroxide solution^ increase of the concentra­

tion of the inhibitor from 0.01% to 2.0% brings about only

X^'X^S tliree percent additional protection and in 0.5N

sodium hydroxide solution^inhibition is practically the

same (98%) throughout 0.01% to 0.2% concentration of the

inhibitor. Very thin reddish yellow films are formed

over the metal specimens when the % inhibition is between

85 to 99%.

Sodium diethyldithiocarbamate reacts with solutions of

copper salts to give brownish yellow coloured compound

having the formula^0

Thiourea! ( TABLE -V-1 E_j F/6 - V - 1 S )

In general, it appears that the efficiency of the inhibi­

tor increases with alkali concentration. Thus, at 0.2%

concentration of thiourea the corrosion of copper in 1.0N, CMqL-

0.5N solutions is retarded to an extent of about 76% and

46% respectively. In the case of 1.0N solution beyond

the concentration of 0.2% of thioureaj the efficiency of

the inhibitor decreases with further increase in concentre"

tion of thiourea. In 0.2N sodium hydroxide solution upto

0.5% concentration of thiourea^the corrosion of copper is

accelerated. The acceleration of corrosion increases with

the decrease in the concentration of thiourea and even at

2% concentration of thiourea^the corrosion of copper is

retarded only to an extent of 23% in 0.2N sodium hydroxide

solution. In 0.5N sodium hydroxide solution, the accelera­

tion of corrosion is observed only at 0.01% concentration

of the inhibitor. In general, the metal specimens were

covered with very adherent black films.

Thiourea reacts with cupric ions to form a white precipi­

tate in acidic media and a brown precipitate in an

• j -I
ammonical media. According to Horner et.al. , Thiourea

forms zujiitter ions in alkaline solution according to the

reaction

S
e OH

and adsorption of ^witter ions might be responsible for its

inhibitor action towards copper i n ,alkali^which explains

the fact that inhibitor efficiency increases with increase

in alkali concentration.

Dithio-oxamide• CTABLE V IE , V 1 H)

The inhibition of the corrosion of copper is maximum in

1*0
0.2N and 0.©N sodium hydroxide solutions at a concentre-
'o ®*S
tion of 0.4% of dithio-oxamide. whereas in sodium

hydroxide solution^the maximum inhibition is obtained at

0.03% concentration of dithio-oxamide. The corrosion of

copper is retarded in 0.2N, 0.5N and 1*0N sodium hydroxide

solutions to the maximum extent of about 26%, 77% and 66%

respectively at the optimum concentration mentioned above.

When the concentration of dithio-oxamide is increased

beyond the optimum concentration/the protective power of

dithio-oxamide falls off and in 0.5N and 1.0N sodium

hydroxide solutions^the corrosion is accelerated to an

extent of about 250% and 406% respectively by the addition

of 0.5% of dithio-oxamide. In 1.0N sodium hydroxide, the

acceleration of corrosion at high concentration of

inhibitor is to a much greater extent'as compared to that

in 0.5N and 0.2N sodium hydroxide solutions. Thus, it

appears that the dissolution of the complex formed over

the metal surface is facilitated by high alkali concentra­

tion. It will be interesting to state here that in the

case of brass (70/30)^ the corrosion is prevented almost

completely at 0.1% concentration of dithio-oxamide in 0.2N

 ft fp

0.5N and 1,0N sodium hydroxide solutions. Moreover,

there is no adverse effects of the excess of inhibitor

on its efficiency. This difference may be due to the

presence of zinc in the alloy and the complex formed

with zinc may not be susceptible to high alkalinity or

to the high concentration of the inhibitor. The metal

specimens were covered with thick black films.

The black copper complex of dithioxamide can be written

as72

HN C - C NH
i I
\ /

It is insoluble in ammonia and dilute mineral acids.

Formation of thick black films on copper specimens was

noted confirming the formation of eu-dithioxamide complex.

Sodium-chromotropate • C TABLE V 1 C} F IB . V 1 E)

In 0.2N sodium hydroxide the corrosion of copper is

retarded to an extent of about 66% by the addition of

0.005% concentration of inhibitor. With further increase

in the concentration of the inhibitor^ protective power falls

off. In 0.5N sodium hydroxide solution^the corrosion is

retarded to an extent of about 66% at 0.5% concentration of

the inhibitor Thus the protective film is formed at lower

concentration of the inhibitor in 0.2N sodium hydroxide

solution. In 1.0N sodium hydroxide solution there is

an acceleration of corrosion at 0.001% concentration of

fck>- ■
the inhibitor and corrosion is retarded to an extent of
A
74% at 0.2% concentration of the inhibitor, and as in the

case of 0.2N sodium hydroxide solution^ kere also a

further increase of the concentration of the inhibitor

protective power falls off. Thin reddish brown films

are formed over the metal specimens at optimum concentra­

tion of the inhibitor.

Sodium rhodizonate : C TfiiBLB -V- ± C , flG -V- I D )

At 0.1% concentration of the inhibitor^ the corrosion of

copper in 0.5N sodium hydroxide solution is retarded to

an extent of about 90%. In 0.2N'and 1.0N sodium hydroxide

solutions^ the maximum inhibition (87% and 80%) is obtained

at 0.2% concentration of the inhibitor. As found with

some inhibitors.the excess amount of inhibitor has no

J
adverse effect on the efficiency of the inhibitor. It is

interesting to compare the results obtained in 0.2N, 0.5N

and 1.0N sodium hydroxide solutions at the inhibitor

concentration of 0.001%. At this concentration of the

inhibitor^corrosion of copper is retarded only in the case

of 0.2N sodium hydroxide solution (39% inhibition). At

0.1% and 0.2% concentration of inhibitor^ thin reddish

yellow films are formed over the metal specimens, y Sodium

rhodizonate reacts with cupric ions to give an orange red

precipitate in neutral media. The complex may be written

Gallocyaninei '‘C TABLE-\J~X p)

Very thin brown films are formed over the metal surface

and this film appears to be protective. The corrosion of

copper is inhibited to a greater extent in higher alkali

concentration (0.5N and 1.0N). The effect of alkali

concentration is visualized by comparing the results obtained

at 0.01% and 0.05% concentration of the inhibitor. In the

0.05% has no effect,. 94 to 95% inhibition is ach[pved

in 1.0N and 0.5N sodium hydroxide solutions by the addition

of 0.05% and 0.1% of the inhibitor respectively whereas in

the case of 0.2N sodium hydroxide solution^ even the

addition of 0.2% concentration of the inhibitor brings

about 86% protection. There is no acceleration of

corrosion at very low concentrations and also no falling

off of the protective power at high concentration of the

inhibitor. At 0.001% and 0.01% of inhibitor concentra­

tions thick brown films are formed over the metal surface

and at higher concentrations of the inhibitor very thin

brown films are formed over the metal specimens,

Acriflavine* C TABLE - V - j, G )

Acriflavine is also a good inhibitor. In 0.2N and

0.5N sodium hydroxide solutions corrosion is retarded

to an extent of about 92 to 94% and in 1.0N sodium

hydroxide solution to an extent of about 86%, At any

concentration of the inhibitor, the inhibitor functions

more efficiently in 0.5N sodium hydroxide solution as

tk d L
compared to in 0.2N and 1.0N sodium hydroxide solutions,
h
This is very well illustrated at 0,001% concentration of

the inhibitor. At this concentration of the inhibitor

the corrosion of copper is retarded to an extent of about

42% in 0.5N sodium hydroxide and in 0.2N'sodium hydroxide

solution, there is no protection at all, and in 1.0N

‘ /

sodium hydroxide solution^it is only about 5%. Very

thin yellow film is formed over the metal surface in the

presence of acriflavine and which affords protection to

copper.

Quinalizarin* ( TABLE V 1C ? FlG VIE)

At 0.01% concentration of the inhibitor^ the corrosion of

copper is inhibited to a greater extent in 0.2N sodium

hydroxide solution. Thus it appears that the film of

product formed over the metal surface at 0.01% concentra”

tion of the inhibitor is more stable in dilute alkali.

There is no critical range of concentration beyond which

the protective power decreases with the increase in the

concentration of the inhibitor as has been observed with

cupron. At 0.5% concentration of quinalizarin,the

corrosion of copper in 0.2N, 0.5N and 1.0N sodium

hydroxide solutions is retarded to an extent of about

82%, 91% and 91% respectively.

Between 65 to 90% inhibition^brown films are formed over

the metal specimens turning- red with sulphuric acid

Furfur aldehyde • (.TABLE V IF }

This is an excellent inhibitor for copper in alkali

solutions. As little as 2.17 ml/l of furfuraldehyde

brings about 100% protection. The inhibitory effect of

furfuraldehyde increases with increase in the concentra­

tion of alkali which is very well reflected at 0.43 ml/l

concentration of furfuraldehyde. In 0.2N, 0.5N and

1.0N sodium hydroxide solutions^the retardation of the

corrosion of copper is to an extent of 68%, 99% and

practically 100% respectively. More over there is no

tendency of the inhibiting power of the inhibitor to

fall off with increase in the concentration of furfural­

dehyde beyond a concentration of 0.43 ml/l. Furfuraldehyde

has been found by u s a n excellent inhibitor for copper

in acids, alkalies, ammonium chloride solutions, neutral

solutions etc The inhibitive power of furfuraldehyde

appears to be due to the formation of resinous product

which is adsorbed over the metal surface to form a

protective layer.

2, 4 Pentanedione * ( TABLE V i D 3 Ei Q V 1. F)

2, 4 Pentanedione is proved to be a very weak inhibitor.

In the case of 0.-5N and 1.0N sodium hydroxide solutionSj

the corrosion of copper is retarded only to an extent of

about 30% by the addition of 26.10 ml/l of 2, 4 Pentane­

dione. Interesting results are obtained in 0.2N sodium

hydroxide solution. Upto 8.70 ml/l concentration of

2, 4 Pentanedione^the corrosion of copper is accelerated

to an extent of 40%. This suggests that the soluble

complex is formed under this condition. At critical

concentration of <17.4 ml/l) 2, 4 Pentanedione^ the

corrosion of copper in Q.2N sodium hydroxide solution is

retarded to an extent of 53%. Again, as the concentra­

tion of the inhibitor is increased beyond the critical

concentration, the corrosion of copper in 0.2N sodium

hydroxide solution is accelerated to an extent of 53%.

Acetone* C TABLE V i F 10 V 1. F}

Acetone is not an efficient inhibitor. As compared to

its action in 0.5N and 1.0N sodium hydroxide solutions,

the corrosion of copper is retarded to a greater extent

in 0.2N sodium hydroxide solution.

 Cyclohexanone! C TABLE - V- 1 f, f/6- V - l fi)
' tin.?'
Cyclohexanone retards'corrosion of copper in 0.5N sodium
A
hydroxide solution to a greater extent as compared to that

in 0.2N and 1„0N sodium hydroxide solutions. If we

’compare the results obtained with 2.17 ml/l con cent ra­

tion of cyclohexanone^ it will be seen that the corrosion

of copper in 0.2N, 0.5N and 1.0N solutions is retarded

to an extent of about 66%, 91% and 89% respectively. At

(§} concentration of 26.10 ml/l^the corrosion of copper is

retarded to an extent of 90%, 95% and 90%, respectively.

Beyond 8.70 ml/l concentration, there is not much

difference in the protective power of Cyclohexanone,

Hydrazine sulphate! C TABLE ~ 3 -^ y ^ 1 I ^

At 0.01% concentration of the inhibitor^ the corrosion of

copper in 0.2N alkali is retarded to a greater extent

(73%) than that in 0.5N alkali (33%) and in 1.ON alkali

(36%). ' At 0.05% concentration of the inhibitor, the

corrosion is practically inhibited completely. At 0.05%

and 0.1% concentration of inhibitor, metal specimens were

covered \<rith a very thin brown films.

Glucose: t TABLE V 1 J> , FV6 V IF)

Upto" a concentration of 0.2% of glucose_,the retardation of

the corrosion of copper is to a greater extent in 0.5N

sodium hydroxide solution as compared to 0.2N and 1.0N sodi

hydroxide solutions and at 1% concentration of glucose

 there is practically no corrosion of copper at all the

three concentrations of alkali studied. It is interest­

ing to note that 0,05% concentration of glucose,there is

no inhibition of the corrosion of copper in 0.2N sodium

•0
hydroxide solution. Thick brown, thin brown and very

thin brown films were noticed on the metal specimens

depending upon the % inhibition. The probable explana­

tion for the powerful inhibiting action of glucose is that

it removes the dissolved oxygen from the solution by a

reaction which is catalyzed by copper. Cupric copper is

reduced to cuprous copper by glucose. Cuprous copper is

readily oxydized to cupric state by dissolved oxygen so.

that the solution becomes oxygen free} such an explanation

was put forth by R a d l e y 18 in explaining the inhibitory

action of glucose on the corrosion of copper in ammonia.

Tannin * ( TA BL E V I S )
The efficiency of tannin increases with increase in alkali

concentration. The protective effect of tannin in

solutions of relatively high pH seems to be associated with

film formation, Upto 1% concentration of tannin, its

protective power increases with alkali concentration.

However, as the concentration of tannin is Increased from

1% to 2%, its efficiency in 1.0N sodium hydroxide solution

decreases by about 22%. In this respect, it resembles

This may be associated with the

fact that tannins may act as oxygen adsorbers, with resultant

 '4 a n

ring opening of the catechol and pyrogallol nuclei which

they contain to form alib^atic acids. Sodium pyrogallol

A

is well known as an efficient oxygen a&’

sorber and tannins

are capable of giving rise to compounds very similar to

pyrogallol in alkaline conditions. Tannins have no

tendency to absorb oxygen in acid or neutral solutions,

but excess alkalinity results in a rapid rise of absorption

powers, which reach a limiting value at higher alkaliniti.es.

There appears to be strong evidence, therefore, ishat

dissolved oxygen will be taken up by tannin. At lower

concentrations of the alkali, complete inhibition has not

been observed, although the presence of tannins reduces

the amount of corrosion. This postulation is supported

by our observation that under these conditions, darkening

of the solution occured and this is usually associated winh

oxygen absorption. Tannin reacts with a number of catiois

and anions to form products. It is reported in literature

that copper reacts with tannin only upon the addition of an

alkali. Thus in the present work in alkaline medium, it

is quite possible that the inhibitory action of tannin in

alkali is due to the formation of a thin film of the

reaction product on the surface of the metal and the stabi­

lity of the film depends on the alkali concentration and on

the concentration of the inhibitor.

Between 75% and 90% inhibition the metal specimens were

covered with thin reddish films

MOLECULAR STRUCTURE OF PHENOLS AND
THEIR INHIBITOR ACTION

Effect of change of nucleus •

To investigate the effect of nucleus to which phenolic

-OH group is attached, the retardation of corrosion of

copper hy phenol, 0^,-naphthol, ^ -naphthol and

8-quinolinol has been investigated. The results are

plotted in Fig^E-2. All the four substances give good

protection to copper in sodiumhydroxide solutions. The

order of efficiency b e i n g ^ napthol > Phenol — g-hydroxy-

quinoline yj-n aphthol.

The protective action of { ^ —napthol and ^ -napthol appears

to be due to the formation on the metal surface of complex

compounds which dissolve with difficulty and thus insulate

the metal, slowing down corrosion. It appears that the

film of complex product is more stable in dilute alkali

(0.2N) when the concentration of g^-napthol used is 0.01%

with a result the inhibition is to a greater extent in

0.2N sodium hydroxide solution, whereas in the case of

^ -napthol it appears that upto 0.5% concentration of the

inhibitor, the stability of the film formed of complex

product on the metal surface increases with the decrease

in the concentration of the alkali and as a result the

inhibition increases with the decrease in the alkali

concentration. In the case of 0 L> “napthol when its con­

centration is raised to 0.5% the stability of the film is
maintained equally well in all the three concentrations

of alkali so that the retardation of the corrosion of

copper is practically equal in all the three alkali

concentrations, 8~hydroxyquinoline is a wellknown

chelating agent. Its copper chelate is precipitated in

the pH range 5.33—14.55. .The complex can be represented

by the structure

Another important aspect worth Investigating is the

effect of substituents in phenol in ortho meta and para

positions with respect to the phenolic -OH group, in

inhibiting the corrosion of copper in sodium hydroxide

solutions. With this airn^ compounds having methyl,

aldehyde, hydroxyl, amino and nitro groups as substituents

in phenolic nucleus were studied. As indicated from the

action of salicylaldehyde, m-cresol and p-nitrophenol in

inhibiting the corrosion of copper in sodium hydroxide

solution, the introduction of an aldehyde, nitro, or a

methyl group in phenol is not very beneficial to inhibitor

action. Hence the corresponding compounds having these

substituents in other positions were not investigated.

 Effect of ortho substitutions

To investigate the effect of ortho substituents in

phenol on the inhibitor action, catechol, o-aminophenol,

salicyladehyde and pyrogallol were studied. The results

..are plotted in Fig.F'3. It can be seen that: salicylal-

dehyde is not an effective inhibitor for the corrosion of

copper in sodium hydroxide solutions. The introduction

of an amino or hydroxyl group in ortho position brings

about interesting results, o-aminophenol, catechol and

pyrogallol are effective inhibitors of the corrosion of

copper in sodium hydroxide solutions at inhibitor

concentrations ranging from 0.009 to 0,010 g/mol/l,

however, with further increase in inhibitor concentration,

the efficiency decreases and even the corrosion is

accelerated at times. A similar effect was observed in

the case of inhibition of the corrosion of 63/37 brass in

sodium hydroxide solutions by catechol and o-aminophenol*

however in the case of pyrogallol, the protection afforded

to 63/37 brass did not decrease with the increase in the

inhibitor concentration.

It has been suggested by Putilova, et.al17 that at higher

concentrations, many organic substances retard corrosion to

a lesser degree and some times becomes accelerators of

- corrosion. It is possible that in the present case, at

\

r higher inhibitor concent rations, the reaction between the

metal, the inhibitor and the corrosive medium becomes

 }

449

easier, creating conditions for the formation of distinct

compounds as opposed to surface compounds. Thus, more

metal is used than at low concentrations of the inhibitor,

when the amount of inhibitor is insufficient to form this

compounds.

The chelate compounds of copper with the abovementioned

phenols can be represented by the following structures!

PYROSALL ol . C A T E CH O L O - AMI NOPHENOL .SftUCYMLDEHWE

In fact, we did observe that the metal specimens are

covered with films in presence of all the four inhibitors »

at inhibitor concentrations corresponding to effective

inhibition.

Interesting results are obtained with pyrogallol.

Dobereiner^® was the first to observe that oxygen is

absorbed by an alkaline solution of pyrogallol. Wenger

and co-workers have.studied the reactions of pyrogallol

with various cations and suggested that Cu+ and Cu++ ions

are reduced to the metal. Thus, at. the first sight it

may appear that reducing property of pyrogallol is respon­

sible for the inhibitive action. If we study closely the

 results obtained in the present work, it will appear

that it is not the sole reason. The proportion of

dissolved oxygen is greater in dilute solution than

that in concentrated solution and hence it is likely that

in O.SN and 1.0N sodium hydroxide solutions 80 to 82%

inhibition is attained at low concentrations of the

inhibitor (0.2%) and for the same percentage protection

of copper in 0.2N sodiumhydroxide solution^1% concentra­

;/

tion of the inhibitor is required. The question now

arises as to the decrease in the inhibiting power of the

inhibitor in 0.5N and 1.0N sodium hydroxide solutions

beyond the concentration of 0.2% of the inhibitor. If

the function of the inhibitor is connected only with the

removal of the dissolved oxygen then increase in the

concentration of the inhibitor in 0.5N and 1.0N sodium

hydroxide solutions should not be accompanied with

decrease in the protective power of the inhibitor. It

/■' appears that in the present case^ the inhibition is also

due to the formation on the metal surface of a thin

insoluble layer of products of reaction between the metal,

the inhibitor and the ions of the corrosive medium and it

is quite possible that at higher alkali concentration with

increase in the concentration of the inhibitor the

reaction between it and the metal becomes -easier creating

conditions for the formation of distinct compounds as

opposed to surface compounds. It is also possible that

the falling off of the protective action at higher alkali

concentration is probably connected with the formation

of compounds more soluble under these conditions. It

may, however, be mentioned that the cause of such a

falling off of the protective action with change of

inhibitor concentration is not always clear.

Effect of meta substitution!

To investigate the effect of meta substitution in phenol

oi| the inhibitor action m-cresol, m—aminophenol,

resorcinol and phloroglucinol were studied. Results

are plotted in Fig.Y-4. From this figure it can be seen

that while introduction of an amino or a hydroxyl group

in m-position is beneficial, the introduction of a

methyl group is not so. Resorcinol is thus an excellent

inhibitor which affords ^ 99% protection to copper in

all the alkali concentrations studied. Contrary to the

ortho substituted compounds, the inhibitor action of

a_-
resorcinol is not adversely ^ffeeted by increasing its

concentration. In the presence of resorcinol( copper

specimens are covered with reddish yellow coloured films

which indicate^ that the protective action of resorcinol

is due to film formation.

Effect of para substitution!

To investigate the effect of para substitution in phenol

on inhibitor action, hydroquinone, p-aminophenol and

y.
p~nitropheno 1 were studied.- Results are plotted in Fig^5.
It seems that the protection afforded by phenol to copper

in sodium hydroxide solutions is not due to the acidic

strength of the phenol. The introduction of a nitro

group in para positions to the phenolic hydroxyl group

greatly increases the acid strength of phenol as is

evident from the fact that ionization constant of para*

nitrophenol is about thousand times greater than that of

phenol^9. However, as can be seen from Fig 3£'5 para

fi
nitrophenol does not effectively retard the corrosion of

copper. Moreover the lowering of the acidity, e.g. by

an introduction of a methyl group in the phenol nucleus

is also not effective in retarding the corrosion as can

o n
be seen from the study of m—cresol •
/

In the case of p-aminophenol and hydroquinone^the

mechanism of inhibitor action is rather complicated by the

fact that these compounds possess chelating as well as

reducing properties. As can be seen from Fig JjS-5, both

the substances are effective at 0.009 g/mol./l.concentra­

tion and with further increase in inhibitor concentration,

their efficiency decreases.

Effect of the position of OH group!

FigJE-6 shows the effect of the position of -OH group in

dihydric and trihydric phenols on their inhibitor action.

The highest efficiency is shown by the m-substituted

phenols namely resorcinol and phloroglucinol Of the

dihydric phenols studied, resorcinol is normally consi­

dered to be the most reactive even if it is oxidised

with more difficulty and it more easily gives tautomeric

keto forms which are more polar®-*-. A study of

phloroglucino1 which is symmetric confirms the proper-

tie’s of resorcinol. Phloroglucino1 gives excellent

inhibition even at as low a concentration as 0.004 g/mol./l

and beyond that its efficiency does not decrease. The

structural formula of phlo roglucino 1 is represented by8<i

OH

and it is probable that under the conditions of study,

the triketo form gets adsorbed over the metal surface by

virtue of its carbonyl groups. The dipole moments of

phenols are! phenol 1.7, catechol 2.62, resorcinol 2.07j

hydroquinone 1.4s3. The corresponding values of

dissociation constants®^ are! phenol 9.95, catechol

9.14, resorcinol 9.14, hydroquinone 9.73. Thus, no

correlation is observed between these properties and

their inhibitor action. '

Effect of the position of,NH 2 group!

FigE-7 shows a comparison of the performance of o“ m- and

p-aminophenols. Just as in the case of -OH group, in

the case of amino group also, m- substituted compound

is most effective in retarding the corrosion of copper

in sodium hydroxide solutions.

o—aminophenol forms a copper chelate having the structure

whereas the inner complex of ^aminophenol with Cu can be

/
written as85

It seems that the chelates formed do not form a protective

film on copper surface.

Conclusions 5

Table 2 shows a comparison of performance of inhibitors^

evaluated in 0.2, 0.5 and 1.0N sodium hydroxide solutions

 4S 5
at effective inhibitor concentrations. Furfuraldehyde

is the best inhibitor which protects copper completely

at all the alkali concentrations studied. The next in

order of efficiency is hydrazine sulfate. Glucose,

resorcinol and sodium diethyl dithiocarbamate are

excellent inhibitors.

Of the substances studied, catechol, o“aminophenol,

salicylaldehyde, ^naphthol, |S naphthol, 8~quinolinol,

sodium rhodizonate, sodium chromatropate, 2,4 pentane-

dione, sodium diethyldithioearbamate, thiourea,

dithioxamide, Supferron and cupron exert their inhibitor

action by formation of chelates. Consequently, the

protection afforded by these substances depends on the

stability, solubility, adhesivity and impenetrability of

the film of cupric chelates covering the metal surface.

Glucose, hydrazine sulphate and hydroquinone inhibit the

t-U«&
corrosion of copper in alkali by reducing action.

Pyrogallol and hydroquinone behave similarly in the sense

that in l.ON alkali when the concentration is increased

from 0.2 to 1.0%^the protective power of both these

substances falls off. - The falling off of the protective

power is much more with pyrogallol as compared to

hydroquinone. Hydrazine sulphate is far more efficient

amongst the reducing agents and brings about complete

protection at a concentration of 0.05%. Then comes

glucose which affords complete protection to copper in

 i § S'

0.2N, 0.5N sodium hydroxide solutions at 0.5% concen­

tration of glucose. In 1.0N sodium hydroxide

solution, the concentration of glucose required to

bring complete protection is 1.0%. In general, the

order of efficiency of these substances is hydrazine

sulphate y glucose y hydroquinone.

The mechanism of inhibition of the corrosion of copper

in alkaline solutions by pyrogallol and p-aminophenol

is rather complex due to the fact that these

substances are reducing agents as well as chelating

agents, and their inhibitor action is dependent on both

these properties.

Resorcinol, phloroglucinol, m-cresol, m-aminophenol,

p-nitrophenol, furfuraldehyde, acetone and cyclohexanone

exercise their inhibitor action by adsorption of the

inhibitor (or the reaction product of the inhibitor with

medium and cupric ions) over the metal surface.

 q ft y

TABLE V - 1 : EFFICIENCY (%) OF INHIBITORS

IN SODIUM HYDROXIDE

D u ra tio n : 5 days Tem perature ; 35° C.

0.2N 0.5N l.ON

I n h ib i to r Loss I n h ib i- Loss % I n h ib i - L oss- % I n h ib i­

Concn.% mg/dm* t io n m g/dnr tio n m g/dnr tio n
ml/1 .

1. PHENOL i

0 .0 0 m l/1 5 6 .8 12 0 .8 1 1 0 .8
2 .1 7 6 .6 88.4 5 6 .5 53.2 7 .8 9 3 .0
4 .3 5 5 .3 9 0 .7 10.0 9 1 .7 7 .8 - 9 3 .0
8 .7 0 4 .7 9 1 .7 9 .9 9 1 .7 6 .6 9 4 .1
1 7 .40 0 .3 9 9 .5 7 .8 9 3 .6 5 .3 94 .2
.26.10 0 .3 9 9 .5 6.1 9 5 .0 4 .4 9 6 .0

2. CATECHOL :

0.00% 5 6 .8 _ 1 2 0 .8 [ _ 1 1 0 .8
0 .0 1 5 6 .8 8 7 .3 2 7 .7 8 9 .5 1 9 .3
0 .1 0 1 5 .5 7 2 ,7 13.0 89.2 - 1 8 .8 83.0
0 .2 0 17.2 69 .8 2 1 .3 82 .3 2 2 .4 7 9 .7
0 .5 0 2 1 .6 61.9 42 .9 64.5 56 .0 4 9 .5
1 .0 0 5 7 .7 -1 .4 1 02.0 32.1 89.2 19 .5

3. BESOBCINOL :

0.00% 5 6 .6 _ 1 2 0 .8 mt 1 1 0 .8
0 .0 1 3 5 .7 37.1 5 6 .5 5 3 .2 9 .1 9 1 .8
0 .0 5 5 .3 9 0 .7 5 .3 9 5 .6 9 .1 9 1 .8
0 .1 0 3 .9 9 3 .2 5 .0 9 5 .8 7 .8 9 3 .0
0 .2 0 3 .9 93 .2 5 .0 9 5 .8 7 .8 9 3 .0
0 ,5 0 2 .8 95.1 3 .6 9 7 .0 6 .4 9 4 .2
1 .0 0 0 .5 9 9 .0 0 .8 9 9 .4 0 .8 9 9 .3

4. HYDBOQUINONE :

0.00% 5 6 .8 _ 1 2 0 .8 a* 1 1 0 .8
0 .0 5 3 6 .6 3 5 .6 4 6 .0 6 1 .9 2 6 .3 7 6 .3
0 .1 1 4 .7 74.1 16.9 85.9 19.4 8 2 .5
0 .2 7 .5 8 6 .8 11 .6 9 0 .4 1 6 .6 85.0
0 .5 3 .6 9 3 .7 1 0 .8 91.1 19.4 8 2 .5
1 .0 2 .2 9 6 .1 6.9 9 4 .3 2 4 .4 78 .0
 T /m E - V * 1 A
0.2N 0.5N l.ON

I n h ib ito r
Loss % I n h ib i- Loss % In h ib i- Loss % In h ib i­
Concn.% tio n mg/dm^ tio n mg/drn^ tio n
mg/c
ml/1

5. PYBOGALLOL :

0.00% 56.8 ,120.8 110.8 _

0.01 27.7 51.2 101.1 16.3 Mi
0.10 22.2 60.9 24.1 80.1 23.6 78.7
0.20 22.2 60.9 24.1 80.1 19.4 82.5
0.50 19.4 65.9 66.2 45.2 39.8 64.5
1.00 10.0 82.4 76.7 36.5 77.6 30.0

PHLOBOGLUCINOL •
*

0.00% 56.8 120.8 110.8

0.001 33.4 41.2 148.8 -2 ^ 5 89.7 19.0
0.01 31.9 43.8 101.1 16.3 62.6 43.5
0 .0 5 10.0 82.4 11.6 90.4 15.5 86.0
0 .1 4.2 9 2 .6 5 .6 95.4 12.2 89.0
0.2 2 .8 95.1 5 .6 95.4 12.2 89.0

m-CRESOL :

0 .0 0 m l/l 56.8 120.8 110.8

2 .1 7 45.7 197s 96 .7 19l9 63.2 4 3 .0
4 .3 5 41.0 2 7 .8 77.8 35.6 46.5 58.0
8.70 30.7 45.9 54.6 54.8 35.7 67.8
17.40 15.2 73.2 33.2 72.5 27.4 75.3

m-AMINO PHENOL •
•

0.00% 56.8 12 0 .8 . 110.8

0.01 31.9 43.~8 103.6 U.2, 60.9 45 .0
0 .0 5 16.6 70.8 81.2 32.8 24.1 78.3
0 .1 12.1 78.7 2 1 .0 82.6 16.1 85.5
0.2 7 .6 86.6 15.5 87.2 10.0 90.9
0 .5 7 .6 86.6 7 .5 9 3 .8 10.0 90.9

9. p-AMINO PHENOL :

0.00% 5 6 .8 12 0 .8 110.8
0.001 55.1 3 .0 83.0 31 .3 70.6 3 6 .3
0.01 35.7 37.1 50.4 58.3 37.1 66.5
0 .0 5 21 .8 61.6 14.7 87.8 12.8 88.4
0.1 12.2 78.5 12.5 89.7 11.1 90.0
0 .2 18.6 67.3 15.5 87.2 15.3 86.2
0 .5 36.0 36.6 31.0 74.3 26.3 76.2
 $ B 53i ,
TABLE -V - I B
0.2N 0.5N l.ON

I n h ib ito r Loss % In h ib i- Loss % I n h ib i- Loss % In h ib i-

Concn.% mg/dm2 tio n ’mg/dn£ tio n mg/ctoi^ tio n
■1/1

10. p-NITBO PHENOL :

0.00% 56.8 120.8 110.8

0.01 42.9 24.5 120.8 . 0 .0 110.8 0 .0
0 .0 5 38.8 31.7 105.3 1 2 .8 9 2 .5 16.5
0.1 36.0 36.6 104.0 13.9 85.9 2 2 .5
0 .2 36.0 36.6 9 8 .6 18.4 79.0 28.4
0 .5 24.9 56.2 9 5 .8 20.7 7 2 .6 34.5

11. SALICYLADEHYDE •
•

O.OOml/l 56.8 120.8 110.8

2.17 32.9 42a 117.2 3 .0 87.8 2 0 .8
4 .3 5 30.2 46.8 110.8 8 ,3 84.8 2 3 .5
8.70 26.0 54.2 98.0 18.9 84.8 2 3 .5
17.40 26.0 54.2 81.7 32.4 76.7 30.8
26.10 6.6 88.4 62.9 47.9 76.7 30.8

12. oC -NAPTHOL ;

0 .0 0 % 56.8 120.8 110.8

0.01 2 6 .3 53a 92.2 2 3 .9 88.6 2 0 .0
0 .0 5 24.9 56.2 85.0 29.6 67.0 39.5
0.1 24.9 56.2 34.3 71.6 31.0 72.0
0 .2 14,4 74.7 2 3 .8 80.3 2 3 .8 78.5
0 .5 11.1 80.5 19.4 83.9 2 1 .6 80.5

13.- {i-NAPTHOL :

0.00% 56.8 120.8 110.8

0.05 33.2 41~b 68.1 4 3 .6 32.1 71.0
0 .1 33.2 41.6 44.6 63.1 32.1 71.0
0 .2 19.4 65.9 22 .7 81.2 19.9 82.5
0 .5 1.4 9 7 .3 13.3 89.0 18.3 83.7
1 .0 0 .3 9 9 .5 5 .8 95.2 2 .8 97 .5
2 .0 0.00 100.0 0.00 100.0 0 .3 99.7
 table - V* 1C.
0.2N 0 .5N 1.,ON

Inhibitor
Conot % Loss % Inhibi­ Loss % Inhibi­ Loss % Inhibi­
ml/1 m g /d m 2 tion m g /d n .2 tion m g /d m 2 tion

14. 8-QUIN0LIWL •
«
0

0.00 % 56.8 120.8 110.8

0.01 67.3 -18.5 95.9 20.6 78.1 29.5
0.05 10.8 81.0 18.8 84.4 62.6 43.5
0.1 10.0 82.4 . 11.6 90.4 17.7 84.0
0.2 7.2 87.3 10.0 ■ 91.7 11.1 90.0
0.5 5.3 90.7 8.3 93.1 13.9 87.5

15. Na_BHODFZONATE ;
/

0.00$’ 56.8 . 120.8 110.8

0.001 34.4 39.4 119.T 1.4 106.7 3.7
0.01 34.4 39.4 100.8 16.6 95.6 13.7
0.05 29.9 47.4 80.3 33.5 73.4 33.8
0.1 27.2 52.1 11.9 90.2 23.3 79.0
0.2 7.5 86.8 11.9 90.2 21.8 80.3

16. Na.CHROMOTBOPATE j •
0.00$ 56.8 120.8 _ 110.8
0.001 37.7 33.6 114.7 5.0 129.9 -17.2
0.005 19.4 65.9 «>. _ —

0.01 25.5 55.1 107.2 11.3 88.6 20.0

0.05 - 30.8 45.8 90.0 25.3 59.8 46.0
0.1 36.8 35.2 69.8 42.4, 34.6 68.8
0.2 52.1 8.3 43.8 59.6 27.7 74.9
0.5 41.6 65.5 47.1 57.5

17. QOINALIZABIN :
0.00$ 56.8 120.8 110.8
0.01 24.7 56.5 65.6 45.9 65.1 41.3
0.05 15.5 72.7 29.1 75.9 35.2 68.2
0.1 14.4 74.7 12.5 89.7 23.3 79.1
0.2 14.4 74.7 11.6 90.4 10.2 90.8
0.5 10.5 81.5 11.6 90.4 10.2 90.8
 4® 1
table- V - 1 £>

0.2N 0.5N l.ON

Losso # In h ib i- Loss % In h ib i- Loss % In h ib i-

ml/1 ° ffl9 / dra<i tio n m.g/dnr tio n rag/dm2 tio n

18. FUBFUBALDEHYDE :

O.GOml/1 56.8 mm 120.8 110.8 •Ml

0 .4 3 18.3 67.8 1 .4 9 8 .8 0 .6 9 9 .5
2.17 0 .0 100.0 0 .0 100.0 0 . 0 100.0
4.35 0 . 0 100.0 0 .0 100.0 0 .0 100.0
8.70 0 .0 100.0 0 ,0 100.0 0 .0 100.0
17.40 0 .0 100.0 0 .0 100.0 0 .0 100.0

19. 8LUG0SE ;

0.00% 56.8 120.8 110.8

0 .0 5 56.8 0 .0 42.7 64.7 44.9 5 9 .5
0.1 35.5 37.5 18.8 84.4 37.1 66.5
0 .2 9 .7 82.9 5 .3 95.6 23.6 78.7
0 .5 0 .5 99.0 0 .5 99.6 9 .7 91.2
1 .0 0 .3 99 .5 0 .3 9 9 .8 0 .8 9 9 .3

20. ACETONE :

0 .0 0 m l/I 5 6 .8 120.8 110.8

2.17 34.3 39,6 111.6 7 .6 9 7 .0 , 12.5
4 .3 5 34.3 39.6 108.0 10.6 9 7 .0 12.5
8.70 33.2 41.6 108.0 10.6 88.6 20.0
17.40 33.2 41.6 104.4 13.6 69.0 37.7
26.10 30.5 46 .3 104.4 13.6 69.0 37.7

21. 2, 4 PENTANEDIONE ;

0.00% 56.8 120.8 110.8

2 .1 7 67.0 -1 8 .0 116.3 3.~7 103.9 6.~2
4 .3 5 79.5 -4 0 .0 109.7 9 .2 101.4 8 .5
8.70 79.5 -4 0 .0 105.3 12.8 87.8 2 0 .8
17.40 26.6 53.2 9 7 .8 19.0 77.8 2 9 .8
26.10 87.0 -5 3 .2 84,2 30.2 77.8 2 9 .8
 4© 2
TAPLE-V-1E
0.2N 0.5N l.ON

Inhibitor Loss % Inhibi- Loss % Inhibi- Loss Inhibi-

Conea.% mg/dm2 tion mg/dm2 tion mg/dnr t i on
ml/1

22. CYCLOHEXANONE ;
O.OOml 'll 56.8 120.8 «• 110.8
2,17 19.4 65.9 10.5 91.3 12.2! 89.0
4.35 8.9 84.3 8,3 93.1 12.2 89.0
8.70 5,6 90.2 8.0 93.4 12.2 89.0
17,40 5.6 90.2 6.6 94.6 11.1 90.0
26,10 5.6 90,2 6.6 94.6 11.1 90.0

'
23. THIOUREA s
0.00"% 56.8 120.8 a* 110.8
0.01 133.0 -134.6 136.8 -13.2 89.2 19.5
0.1 87.8 - 54.6 80.1 33.7 47.6 57.0
0.2 75.6 - 33.1 65.4 45.9 26.9 75.7
0.5 60.7 - 6.9 44.3 63.3 38.8 64.8
1.0 -47.9 15.7 44.3 63. 3 -

2.0 43.8 22.9 - - 44.3 60.0

24. DITHIO-OXAMIDE :
0.00% 56.8 120.8 110.8
0,01 75.6 - 34,9 146.0 -20.9 91.4 17.6
0.02 60.9 - 7.2 34.1 71.7 55.4 50.0
0.03 48.2 15.1 28.3 76.5 52.6 52.5
0,04 42.0 25.9 33.2 72.5 37.4 66.3
0.05 57.6 - 1.41 — 63.4 42.8
0.1 96.4 - 69.7 66,5 45.0 103.0 7.0
0.2 207.0 -264.2 125.2 - 3.6 249.3 -125.0
0.5 210.8 -269.8 422.4 -249.6 561.5 -406.4

25. Na..DIETHYLDITHIOCABBAMATE :
0,00%, 56.8 120.8 m
> 110.8 -

0.001 66.2 - 16.5 126.9 -5.0 96.4 12.7

0.002 88.1 - 55.1 88,1 27.1 100.3 9.5
0.005 8.3 85.4 88.1 27.1 80.9 27.0
0.01 2.8 95.1 2.8 97.7 80.9 27.0
0.05 2.8 95.1 2.8 97.7 6.1 94.6
0.1 2.8 95.1 2.8 97.7 3.0 97,3
0.2 0.8 98.6 1.7 98.6 1.7 98.5
 § o
TABLE - V * 1 F .
0.2N 0.5N l.ON

I n h ib ito r Loss In h ib i- Loss % In h ib i­

% I n h ib i- Loss
Concn«% tio n mg/dm2 tio n
mg/<k2 tio n mg/ctar
ral/1

26. HYDRAZINE SULPHATE :

0.00% 56.8 •M
t 120.8 110.8
0.001 45.4 20.1 90,0 25.5 90.9 18.0
0.01 15.2 73.2 80.6 33.3 70.9 36.0
0 .0 5 0 .3 9 9 .5 3 .6 97.0 0 .3 9 9 .7
0.1 0 .3 9 9 .5 0 .0 100.0 0 .0 100.0
0.2 - 0 .0 100,0 0 .0 100.0

. c o p f ^ eI on j

' “V A

0.00% 5 6 .8 120.8 110.8 _

0.001 35.5 31»5 91.4 2 4 .3 53.7 51.6
0.01 30.7 45.9 91.4 24.3 68,4 38.3
0.05 47.9 15.7 77.6 35.8 68.4 38.3
0 .1 54,8 3 .5 77.6 35.8 63.4 42.8
0.2 54.8 3 .5 77.6 35.8 63.4 42.8
0 .5 74 .8 -3 1 .7 7 4 .5 38.3 56,5 49.0

1. CUPBON ;

0.00% 56.8 120.8 110.8

0.001 41.0 27^8 116.9 3.2 110,8 0 .0
0.01 33.0 41.9 39.9 67.0 106.4 4 .0
0 .0 5 1 0 .0 82.4 19.4 83.9 50.5 54.4
0 .1 25.2 55.6 33.0 72,7 67.3 39.3
0 ,2 45.7 19.5 38.8 67.9 90.9 18.0

». GALLOCYANINE «
*

0.00% 56.8 120.8 •m 110.8 *.

0.001 36.6 3SJ6 9 5 .6 20.9 85.0 2 3 .3

0.01 36.6 35.6 66.5 44.9 46.3 58.2
0 .0 5 12.7 77.6 13.0 89.2 6,6 94.1
0 .1 10.3 81.9 6.1 9 5 .0 6,6 94.1
0 .2 8.0 85.9 . 6.1 95.0 6 .6 94.1
 it

TABLE V 1 (5
0.2N 0.5N l.ON

I n h ib ito r
Concn.% Loss % In h ib i- Loss % InhibL . Loss % In h ib i­
ml/1 mg/dm2 tio n mg/dni2 tio n mg/dm2 tio n

30. AGRI FLAVINE:

0,00% 56,8 120,8 110,8 mm

0,001 56.8 0 ,0 70,4 41.7 105,3 5 .0

0*01 8 .3 85,4 9 .9 91,7 74,1 33.1
0.05 4,7 91,7 7 ,8 93.6 12,7 88,5
0,1 4,7 91,7 ' 7 .8 93,6 16,9 84.7

TANNIN;

0.00% 5 6 ,8 120.8 110.8

0.10 30,0 47 ~ 2 29,1 75.9 16,6 85 ,0
0,20 24.9 56.2 29,1 75,9 13,8 87,6
0 .5 0 24.9 56,2 22.1 81,7 11.4 89.7
1 .0 13.9 75.5 16.9 86,0 12.5 88.7
2 ,0 9 .7 82.9 1 5 ,5 ' 87,0 37.4 66.2

32. 0 -AMINOPHENOL:
0.01M 98,9 (9.3) 71.5 (68.4) 45.7 (81,1)
0.02M 100.2 (9 ,3 ) 76.7 (59,9) 45,7 (79.5)
0.05M 127,2 (-1 5 ,9 ) 108,6 (53.5) 79.2 (66.3)
1.0M 176.4 (-7 9 ,8 ) 149.0 (21.9) 141.3 (29,5)
 TABLE PERFORMANCE OF INHIBITORS IN DIFFERENT CONCENTRATIONS OF
SODIUM HYDROXIDE AT EFFECTIVE INHIBITOR CONCENTRATION FOR AN IMMERSION
PERIOD OF 5 DAYS

In h ib ito r 0.5N NaOH l.ON NaOH

I n h ib ito r 0.2N NaOH
Conen,

N il N il 5 6 .8 120.8 110.8
P henol 17.4 m l/1 0 .3 7 ,8 5 ,3
C a te ch o l 0 1.% 1 5 ,5 1 3 .0 1 8 .8
R eso rcin o l 1 0.% 0 .5 0 .8 0 .8
Hydroquinone 1 0.% 2, 2 6*9 2 4 .4
P y ro g a llo l (a) 1% 1 0 ,0 7 6 .7 7 7 .7
(b) 0 2,% 22,2 24.1 19.4
P h lo ro g lu c in o l 0 ,2 % 2,8 5 .6 12.2
m c re so l 17.4 m l/I 15 .2 3 3 .2 2 7 .4 .,&2»
m aminophenol 0 2
,% 7 .6 15.5 10.0
p-am inophenol 0 1
.% 12.2 12.5 11.1
p-nitxcrphenol 0.5% 2 4 .9 9 5 .8 7 2 .6
S a lic y la ld e h y d e 2 6 .1 ml/1 6.6 62 .9 7 6 .7
<L _ n ap th o l 0.5% 11,1 19.4 21*6
-sia p th o l 2% 0 ,0 0 .0 0 .3
Q u in o lin o l 0.5% 5 .3 8 .3 1 3 .9
S odium rhodizonate 0 2 .% 7 .5 11.9 21.8
Sodium c h ro m o tro p ate (a) 0.005% 1 9 .4
(b) 0 ,2 % 52.1 1 4 3 ,8 2 7 .7
Q u in a liz a r in 0.5% 10.5 11.6 10.2
F u rfu ra ld e h y d e 2 .1 7 m l/1 0 .0 0 .0 0 ,0
G lucose 1 % 0 ,3 0 .3 0.8
A cetone 26 .1 m l/1 3 0 .5 104.4 6 9 .0

Contd
In h ib ito r In h ib ito r 0.2N NaOH 0,5N NaOH 1.0N NaOH
Concn.

2 , 4 pentanedione {a) 17,4 ml/1 26,6 97,8 77.8

(b) 26.1 ml/1 87.0 84.2 77.8
Cyclohexanone 17,4 ml/1 5.6 6,6 11,1
Sodium d iethyl d ith io .
carbamate 0 2
,% 0 ,8 1.7 1.7
<JO/
Thiourea & /Q 43.8 44.3 44.3
37.4 «=Jr
Dithioxamide 0.04% 42.1 33,2 CO
Hydrazine su lfa te 0 1
,% 0,3 0 .0 0 ,0 CO
Cupferron (a) 0 001
. % 35.5 91.4 53.7
lb) 0.5% 74.8 74.5 56.5
Cupron 0.05% 1 0 ,0 19.4 50.5
Gallocyanine 0 ,2 % 8,0 16.1 6.6
A criflavine 0*05% 4.7 7.8 12.7
Tannin (a) 0,5% 24.9 22.1 11.4
(b) 2% 9.7 15.5 37.4
 NOJ±J8IHN I / '
LOSS

N O J1IQ IH N I ^

INHIBITOR EFFICIENCY AND 'WEIGHT LOSS.

 ‘^ I N H I B I T I O N LOSS ^3 /d

INHIBITOR EFFICIENCY AND WEIGHT DOSS.

FIG. V- l A

y IN H I B I T f O N
 F IG. V- IB

7. I N H I B I T f O N
/.IN H IB IT fO N

EFFECT OF ALKALI CONCENTRATION AID INHIBITOR CONCENTRATION 01

INHIBITOR EFFICIENCY AED WEIGHT LOSS.
 FIG. V-IC
*4 y L ’

N OJ1 IQIHN J
LOSS

LOG CON.
EFFECT OF ALKALI CONCENTRATION AND INHIBITOR CONCENTRATION ON
INHIBITOR EFFICIENCY AND WEIGHT LOSS.
 FIG. V-ID

t*"
O

o
o
O'

0*
o
O

oo
O

O
^

O
o
r> cm

O'
O • o

O
in
O O
rr>
O
8 - H Y D R O X Y - Q U f N O L lN E

o
g
vwg l<i Vy\^*

co

IN H IB IT IO N
O
o

O
03
O

O
0
<o
O
LOSS

^
O
1
O

O
to

O
O

(O
O
O O
ro

fu
O
—
o
O

—
O
O

80-

6 O-

4 o-

20 *

0
-1*2 -2 * 4
LOG CON.
EFFECT OF ALKALI CONCENTRAION AND INHIBITOR CONCENTRATION ON
INHIBITOR EFFICIENCY AND YfEIGHT LOSS.
 F)G.
«y2
V-ie

'/, IN H IB IT IO N

INHIBITOH .EFFICIENCY AND WEIGHT LOSS.

 FIG. V- I F
'•>

cl Vyj

% INHIBITION

INHIBITOR EFFICIENCY AND WEIGHT LOSS.

 FIG. V- I G

CYCLO HEXANO NE

ry
'^■o^jdrrrt

2 5 O O

-80

IN H IB IT IO N
20
.6 0
LOOS

I 5

lO ■4 O

5 -20 •'

O O

160

120

eo

40

C
_ L
O
-1. 5

log con .
EFFECT OF ALKALI CONCENTRATION AML INHIBITOR CONCENTRATION ON
INHIBITOR EFFICIENCY AND WEIGHT LOSS.
LOSS ^9
FIG. V- IH

%INHIBITION
 FIG.
4f S
V-l I

/. I N H I B I T I O N
LOSS

INHIBITOR EFFICIENCY AND WEIGHT LOSS,

 'Iff

FIG.- V
CATECHOL R E S O R C IN - P H LdR O G L- wv-C RESOL
OL
OCIN0L
1*0 ^ _ .11
. «5=S—*
^ .4
’ / y ^ *1’
o f
60 • \w,J/ °7 *0

40
\ \ p/
20 \\q K .v j* y ,
IO N

z
A
\ v oj>
O
O , < f — i— »— i— i—
Y%I N H I B I T

0 2 0 6 0 *2 ‘ 0*6 /‘ 0 *2 \ oV6' 0*2 0 *6 t

N O R M A L IT Y (D F v N f r O H CQ
20 X
PY RO GALIO T A N N IN cC-.NAPTHOL ^-N A P T H O L
z
-L
- 2*0*/.
c i^ T o ^ '
POx 0 *2 x , o ^ jL _
80 \ / - a= = Z ^
*& T ~ ~
/ o - i^
60 r\| yS & >
o-yo
X*'
40 . V

NAo

NORMALITY / O F NaOH

0 *2 ‘ 0*6 ' o '* 2 '0 * 6 ‘ 0 *2 ' 0 * 6 ' 0 *2 0 *6 '

EFFECT OF ALKALI CONCENTRATION AM) INHIBITOR CONCENTRATION ON INHIBITOR

EFFICIENCY.
 FIG.-V
ON

• /.IN H IB I T I O N
7 IN H iB IT l
-

EFFECT OF ALKALI CONCENTRATION AND INHIBITOB CONCENTRATION ON INHIBITOR

EFFICIENCY.
 F IG .-V

E U ’ECT OF ALKALI COFCENTBATIOF AUD IffilBITOE CONCENTRATION OF INHIBITOR

EFFICIENCY.
 /

FIG.-V
*>

1-0 * 0 1 X
2-0*0 2 A
♦4 0 0
3-0*0 3 /
4- 0*0 4 *
r3 O O 5\0*0 • '/*
6* 0*0 2 */.
*2 OO 7*•0*057-
/^IN H IB ITIO N

-
d it h io
OXAMfDE
N O R M A L IT Y
OF
N«OH

EFFECT OF ALKALI
CONCENTRATION AMD INHIBITOR CONCENTRATION ON INHIBITOR
EFFICIENCY.
Fig. V-
 OH OH OH
r^SrOH
^/OH
V
PHENOL CATECHOL RE SOR CIN OL

OH OH
H O vA rO H
A - oh

V V"OH VOH
OH
HYDROQUINONE P YR O G A L LO L PH LOR OGLUCINOL

OH OH
aa / A o H

MCH3 w
m-TOLUDlNE ^-NAPTHO L jS-NAPTHOL

O OH O OH
0 ,,/v O N ft

O A in/
I
0rsl4
o HO

SODIUM RHODIZONATE QUINALiZARIN S'HYDROXY QUINOLINE

 if n ft
h w

OH
OH OH
ax „m
s x ,if#,
1 .■•'V X
r" !X
ij
rf
)i
1
A 0 CKa [j
L
i)
i
\) A ;A / > S Q N * N \ /A - 1
A yA h A / ^ N H * H C l O .X V
M H v-* N.-S-3 ^ V H".L X"’ OH
1 ’ *"
‘2. CH 3
i1
c r \ G AL:. O ’X AMINE
AC RJFLAV IN E iO DIUM C HHOM OTOC PAT
CH<> O H
, «-
HO ~C H
f
HO - C - H ,»A
i - “1
H - C ~ OH \
\
r
i
HO - C - H II 1
J CM C A;
CHQ 'V y

GLUCOSE FUR FURAL DE m VDE ** A j S

v f.

OH OH OH
u H.
r
r^ \
l% y km 2
A
1l
H N — C ~ s ■t-i
b
nh*
9-AM I N O PH E N O L m-AMlNQ PHENOL p-ANiSNOPHENOL 1'HIOUHE
CHa
NH !
(Cg h 5)2 = n ~ c s - s n * C\ “ S
co
i
1, ,
C= s ^ ** 2
I
SO DIUM01 ETHYL NH 2 9 0 i
DITH1QC AR BAM ATE c
D ITH IO X 'A WIDE
PENTANE D ioisif
COCH. NO
i H
* 'l A N" 0n h 4 A \- c - c
I >1 It
OH NOH

V % y v*’’

ACETOPHENONE CUPFERRON CUPRON

t A-
f
 4p o

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