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Electronic Theses and Dissertations Theses, Dissertations, and Major Papers

1-1-1967

Dissolution of iron in hydrochloric acid.

Jatinder N. Taneja
University of Windsor

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 DISSOLUTION OF IKON IN HYDROCHLORIC ACID

A Thesis
Submitted to the Faculty of Graduate Studies Through the
Department of Chemical Engineering in Partial Fulfilment
of the Requirements for the Degree of
Master of Applied Science at the
University of Windsor

by

Jatinder N. Taneja

Windsor, Ontario
196?

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 UMI Number: EC52683

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 ABSTRACT

The kinetics of polycrystalline iron dissolution in

nitrogen, air and oxygen saturated hydrochloric acid

(2.^ - 5*37 N) solutions have been investigated. Cylindrical

samples of 0.^7 inches in diameter were rotated at speeds

up to 11,000 r.p.m.

The reaction is half-order with respect to the total

iron concentration in oxygenated and zero-order in oxygen-

free hydrochloric acid solutions. An Arrhenius activation

energy of 9 .^ kcal per gram mole was evaluated for the

temperature range 26° - k5°C,

The dissolution rate in moles of iron dissolved per

litre per hour may be expressed by the empirical rate

equation:

d (F e ) = (A)
3A
(HCl)(exp (- 13.1 + 1.18 x l o V o )°-5(Fe)°
dt V

iii

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 ACKNOWLEDGEMENTS

With great pleasure, I wish to express my sincere

gratitude to Dr. A.' VJ. Gnyp for his valuable guidance and

constructive criticism, to Armco Steel Corporation, Ohio,

U.S.'A., for supplying the analysis of iron, to Mr. Halil Parlar

for machining the iron samples and to a host of friends for

moral support.

Thanks are expressed to Professor R. G. Billinghurst

for supplying the iron rod.

The financial assistance from the National Research

Council of Canada is truly appreciated.

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 TABLE OF CONTENTS

ABSTRACT ili

ACKNOWLEDGEMENTS iv

TABLE OF CONTENTS v

LIST OF TABLES ... viii

LIST OF FIGURES ix

NOMENCLATURE xi

CHAPTER
I.' INTRODUCTION 1

II. LITERATURE REVIEW 3

A. Copper Dissolution 3
B. Tin Dissolution 3
C. Titanium Dissolution 3
D. Corrosion Review of Iron k

1. Action of Mineral Acids on Iron 4-

2. Dissolution of Iron in Perchloric Acid 5
3. Dissolution of Iron in Sulphuric Acid 6
k. Rate of Dissolution in Hydrofluoric Acid 9
5. Rate of Dissolution in Nitric Acid 9
0. Dissolution of Iron in Organic and
Carbonic Acids 10
7. Corrosion of Iron in Hydrochloric Acid 10
8. Oxidation of Ferrous Ions 12
9. Colorimetric Method of Analysis of Iron 15

III. THEORY ’ 17

A,‘ Under AnaerobicConditions 17

B. Aerated Solutions 22

IV.' EXPERIMENTAL 25

A. Materials 25
1. Iron 25
2. Hydrochloric Acid 25
3. Hydrogen Peroxide 25

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 B. Apparatus 25
C. Procedure- 28

V. RESULTS AND DISCUSSION 30

A. General Corrosion Behaviour of Iron 30

B. Dissolution of Iron inOxygen-freeSolutions 30

1. Order of Reaction 30
2. Effect of Temperature and Rotational
Speed on the Dissolution Rate 35
3. Effect of Superficial Area on the
Dissolution Rate 37
4. Empirical Equation 37

C. Dissdlution of Iron in Air andOxygen

Saturated Solutions 40

1. Colour of the Iron Solutions During

Dissolution 40
2. Order of Reaction 40
3
4.
. Reproducibility
Effect of Rotational Speed on the
45

Dissolution Rate 48
5
6.
. Effect of Temperature on Dissolution Rate
Effect of Hydrochloric Acid Concentration
50

on the Dissolution Rate 52

Effect of Superficial Surface Area on the
Dissolution Rate 52
8. Effect of Volume on Dissolution Rate 55
9. Effect of Oxygen on Dissolution Rate 55
10. Empirical Equation 61

VI. CONCLUSIONS 64

VII. SCOPE OF WORK IN FUTURE 66

REFERENCES 68

APPENDIX Typical Analysis of High Purity Iron 71

Supplied by Armco Steel Corporation,
Ohio, U.S.A.

APPENDIX II Colorimetric Determination of Ferric 72

Chloride Concentration

APPENDIX III Detailed Calculations of Constants 76

and Kg in Equation (5.8)

APPENDIX IV 4.027 N HC1 Dissolution Runs 78

APPENDIX V 3.02 N HC1 Dissolution Runs 82

vi

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 APPENDIX VI 5.37 N HC1 Dissolution Runs

APPENDIX VII 6.04 N HG1 Dissolution Runs

APPENDIX VIII 2.4-16 N HC1 Dissolution Runs

APPENDIX IX Effect of Area on Dissolution Rate

APPENDIX X Effect of Volume on Dissolution Rate

APPENDIX XI Effect of Rotational Speed on

Dissolution Rate

VITA AUCTORIS

vJLi

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 LIST OP TABLES

Table ;Page

1-1 Partial Electromotive Series 2

1-2 Hydrogen Ion Concentrations ofAcidic 8

Solutions

5-1 Effect of Rotational Speed ontheDissolution

Rate 4 35

5-2 Effect of Oxygen 60

viii

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 LIST OF FIGURES

Figure Page

3-1 Visual Representation of Polished Surface 18

3-2 Microscopic Representation of Polished Surface 18

3-3 Cubic Crystal Structure on Atomic Scale 19

4-1 Apparatus Arrangement 2?

5-1 Comparison of Ferric Iron Concentrations

Under Different Conditions 31

5-2 Rate of Dissolution of Iron in Air-Free HC1 33

5-3 Arrhenius Plot for 4.027 N HC1 36

5-4 Effect of Superficial Area Under Anaerobic

Conditions J8

5-5 Effect of Acid Concentration Under Anaerobic *

Conditions 4l

5-6 Rate of Dissolution of Iron Under Aerated

Conditions 43
5-7 Effect of Fresh Surface Substitution

5-8 Half Order Plots Under Aerated Conditions 46

5-9 Reproducibility 47

5-10 Effect of Rotational Speed on DissolutionRate 49

5-11 Effect of Temperature on Dissolution Rate 51

5-12 Effect of Acid Concentration Under Aerated

Conditions 53

5-13 Effect of Area Under Aerated Conditions 54

5-14 Effect of Volume on Dissolution Rate 57

ix

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 5-15 Effect of Volume on Dissolution Rate

5-16 Effect of Oxygen on Dissolution Rate

II-l Calibration Curve for Iron Analysis

II-2 Effect of Temperature on Transmittance of

Iron Solutions

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 NOMENCLATURE

(Fe) Total iron concentration, moles/litre

d (Fe)
dt Rate of iron dissolution, moles/lltre-hour

A Superficial surface area of specimen, sq.cm,

V Volume of corroding solution, litres

(HC1) Normality of hydrochloricacid

T Temperature, K°

Pn Partial Pressure of oxygen, atm.

2
kQ Zero order rate constant

ki Half order rate constant

2

t Time, hours

s Surface

b Bulk

i Interface

(i~b) Interface or bulk

R.P.M. Revolutions per minute

K^, K£ Empirical rate constants

xi

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 CHAPTER I

INTRODUCTION

The wastage of metals by corrosion is still a

challenging engineering problem. The fact that millions

of dollars are being spent every year to mitigate such

losses indicates that corrosion control is hardly a reality.

Considerable work still needs to be done on the clarification

of the kinetics and mechanisms by which metals are destroyed

before any effective measures of control may be developed.

Copper (1,2) and tin (5»6) have been subjected to

fundamental investigations. It has been shown that over a

wide range of conditions, the dissolution of these metals

is an autocatalytic process. Naturally it becomes important

and interesting to determine whether other metals capable

of existing in two or more oxidation states show similar

autocatalytic behaviour.

Iron was chosen for the present investigations because

it can exist as Fe++ and Fe+++. It was felt that the

dissolution of iron by simple hydrogen displacement in air-

free solutions would be the same as that of tin and titanium

because all the three metals can liberate hydrogen by

virtue of their positions in the electromotive series as

shown in table 1- 1.

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 TABLE 1-1

PARTIAL ELECTROMOTIVE SERIES

Ti Ti++ + 2e" +1.63 Volts

---- »
Fe — » Fe++ + 2e~ +0.44 Volts

Sn ----- > Sn++ + 2e“ +0.136 Volts

h2 ---- » 2H+ + 2e- 0.00 Volts

Metals, because of their valuable physical properties

of strength and durability, are still the most important

materials of construction. Therefore it is important

that a thorough knowledge of their corrosion characteristics

be obtained. In spite of the considerable contributions made

in the past, there is still a need for further investigation.

The object of this thesis is to study, the corrosion

of iron in hydrochloric acid from the kinetic point of view

with the hope of providing a more quantitative knowledge of

the variables affecting the corrosion rates of metals in

general.

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 CHAPTER II

LITERATURE REVIEW

Considerable work has been done on the study of the

corrosion of copper and tin but comparatively little work

has been done on the corrosion study of iron in hydrochloric

acid. It will be desirable to review briefly some of the

results of the earlier investigators on other metals.

A. Copper Dissolution

Lu and Graydon (1,2) were concerned with the corrosion

of copper in aquous ammonium hydroxide and aquous sulphuric

acid solutions. Weeks and Hills (3) studied the initial

corrosion kinetics in hydrochloric acid solutions and the

same work was extended by Gnyp (4-).

®• Tin Dissolution

Ammar and Riad (5) investigated the rate of corrosion

and corrosion potential of tin in 8 different acid, alkaline

and neutral solutions. A kinetic study of tin dissolution

has been made by Lui (6 ) who rotated cylindrical specimens

in air saturated hydrochloric acid solutions.

C. Titanium Dissolution

The first useful results on the corrosion of titanium

in acids were reported by Gee and Golden (7). Bodner (8 )

studied the kinetics of titanium dissolution in nitrogen,

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 air and oxygen saturated solutions of hydrochloric acid

{2 A - 5-8 N) .

It has been shown that the dissolution of these metals

under appropriate conditions is an autocatalytic process,

with the dissolution rate increasing with increasing metal

ion concentration in the solution.

D. Corrosion Review of Iron

Action of Mineral Acids on Iron

The rates of dissolution of iron in hydrochloric

acid, sulphuric acid and nitric acid were determined by

Schchikow (9) at concentrations ranging from 1 to 10 N.

He found that the rate of dissolution in nitric acid was

comparatively greater than in hydrochloric and sulphuric

acids. Diffusion of cathodically evolved hydrogen was

more intense in sulphuric and hydrochloric acids and was

not absorbed at all by iron in nitric acid.

Hudson (10) made a study of the relationship

between the dissolution rate and hydrogen absorption by

steel as a function of acid selected and of acid concentra­

tion. The study was made by immersing 2 in.x 3/8 in.

coupons for various times in sulphuric, nitric, phosphoric

and hydrochloric acids. Results have been reported at

100°, 1^9° and 19^°F in 0.05, 0.5, 2 and 10 N acid

concentrations. The weight loss atdifferent time intervals

was used as a measure of corrosion and hydrogen content

in the steel was determined by the warm extraction method (11)

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 in which steel specimens were placed in specially constructed

borosilicate extractors and heated for 16 hours at l60°C under

mercury. Hydrogen extracted from the steel by this method

was collected over mercury and measured volumetrically.

Hudson concluded that the rates of dissolution of steel

in 2 N and 10 N solutions of nitric acid at 100°C were much

greater than in other acids of the same concentrations. The

rates of dissolution in 0.05 N and 0.5 N sulphuric acid were

higher than in hydrochloric acid, but in 10 N solutions the

opposite was true. The amount of hydrogen absorbed by steel

during dissolution in nitric acid was much lower than for the

other acids.

Podesta and Arvia (12) also followed the kinetics of

dissolution of polycrystalline iron in acid solutions.

Perchloric acid in sodium perchlorate, hydrochloric acid in

sodium chloride and nitric acid in sodium nitrate were used

for the range of pH between 0 and 6at temperatures ranging

from 40 to 70°C.The rate of corrosion was taken as a measure

of hydrogen ion activity keeping the corrosion potential

constant during the run. They found that for the same range

of pH the corrosion increased in the order CIO^", Cl” , NO^” .

2. Dissolution of Iron In Perchloric Acid

Leko (13) made a study of the dissolution of

iron at 100°C in perchloric acid of varying concentra­

tions under a carbon dioxide atmosphere. The amounts of

4- *4-4- 4~4*4*
H , Fe and Fe were determined. The amount of hydrogen

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 6

gas decreased with increase of perchloric acid concentration;

the decrease being most pronounced between 58$ and 60$

perchloric acid. In 40$ perchloric acid only Fe++ was

obtained. As the acid concentration was increased Fe+++

started appearing and at 58$ perchloric acid the ratio of

Fe++ to Fe+++ became equal to 1. Above 60$ acid only Fe+++

ions were found.

It was suggested that two parallel reactions

occur when dilute perchloric acid is used.

Fe '+ 2H+ >Fe+++ H2

+ 4-J-4-
Jj-Fe + + 8H > k Fe + Cl“ + 4-H20

In concentrated perchloric acid only

8Fe + 3010^“ + 2^H+ — > 8Fe+++ + 3C1" + 12H20

is possible.

3. Dissolution of Iron in Sulphuric Acid

Demon (14) reported on the dissolution rates of

hot rolled and annealed mild steel and carbon steel

(containing 0 .8^ weight percent carbon) in sulphuric acid

solutions (1 to 35.5 N) at 25°C. The main theme of his study

was to find the effect of carbon content and of the acid

concentration on the rate of corrosion of steel in sulphuric

acid. The corrosion rate of five different steels was

determined for thirteen different concentrations of acid

over the range mentioned. In all cases the maximum corrosion

rate decreased between 11 N and 1^ N sulphuric acid. Higher

carbon steels were much more susceptible to corrosion than

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 the lower carbon steels. He found that a steel containing

between 0.06 and 0.37 percent carbon had the lowest corrosion

rate for all concentrations of acid. The steel specimens

became passive in acids more concentrated than 17 N. The

passivating film was shown to be ferrous sulphate.

Archer and Howlette (15) studied the corrosion

of mild steel by sulphuric acid solution over the concentra­

tion range 20.6 to 3^.2 N.

The rate of dissolution of unannealed mild steel

in sulphuric acid solutions (0 .005' to 5 N) was studied by

Whitman et al (16) at 23°C. Whitman’s main purpose was to

find the effect of rotational speed on the corrosion rate.

He explains the theory of the corrosion process this way:

The fundamental equation by which the corrosion

of iron proceeds is

Fe + 2H+ ^ Fe++ + 2H

The rate at which this reaction progresses is

dependent on the following factors:

a. Metal: The corrosion tendency of metal is

determined by its position in the electromotive series.

k* Acidity: Acidity is a measure of hydrogen

ion concentration of the acid. For example the hydrogen-

ion concentrations of 5 N and 2 N solutions of different

acids is given in table 1-2 (17).

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 8

TABLE 1-2

HYDROGEN ION CONCENTRATIONS OF ACIDIC SOLUTIONS

Acid 5N 2N

HNO^ 2.08 1.48 Equivalents

HC1 2.01 1.39 hydrogen ion

h 2s o ^ 1.84 1.01 per litre

H3P0j^ 0.816 0.360

hac 0.013 0.006

c. Ferrous Ion Concentration; According to the

law of mass action the increase in ferrous ions should

decrease the rate of corrosion but this factor seems to

play a minor role.

d. Removal of Hydrogen: This is the most

important factor for the progress of corrosion.

Hydrogen can be removed in two ways

i. By evolution of gaseous hydrogen

2H H2

ii. By depolarization through oxidation

either by dissolved oxygen or by some other oxidizing agent

2H + |02 H20

Gatos (18) reported that the dissolution

of iron in sulphuric acid was increased by ferric ions. He

found that in IN sulphuric acid the dissolution rate in­

creased initially with Fe+++ concentration and then de­

creased beyond 0.4? Fe+++ gm ion/litre and at 4.0 Fe+++ gm

ions/litre, it became approximately equal to the rate in 1 N

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 sulphuric acid containing no Fe+i'+ . The hydrogen evolution

rate decreased with time and with Fe+++ concentrations.

Rate of Dissolution in Hydrofluoric Acid

The rate of dissolution of iron is very high in

dilute hydrofluoric acid (19) (up to H-8% to 50$ HF). In

more concentrated solutions (60$ to 95$ HF) iron is stable.

5* Rate of Dissolution in Nitric Acid

The action of nitric acid on iron is of particular

interest. The attack is very severe at low concentrations

With the products of corrosion being nitrous peroxide (NOg)>

nitric oxide (NO), nitrous oxide (N2O), nitrogen and ammonia.

Whitley and Hallimond (20) showed that the proportion of

N|? + NH^ to NO + NO2 increases if the metal contains in­

ternal Stresses.

Iron exhibits a periodic surface passivation and

activation at concentrations of nitric acid between those

responsible for maximum corrosion and complete passivity.

This 'complex phenomenon has been studied by Vetter (21) and

Bonhoffer (22). They suggested that this behaviour is due

to the formation of nitrous acid during the active period

and its diffusion from the surface into the solution during

the period of passivity.

The powerful oxidizing action of nitric acid will

cause violent attack only if the anodic reaction can keep

pace with the cathodic reaction of the nitric acid. An

increase in the rate of corrosion has been observed in acids

more concentrated than 90$.

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 10

In a way the attack of nitric acid on iron differs

from that on other metals. Any nitric oxide (NO) formed by

reduction of nitrous acid, instead of escaping from the acid,

can be retained,by combination with ferrous salts present,

to form brown nitroso-compounds such as Fe (NO-^^NO, which

remain available for an autocatalytic cycle. The brown

colour generally seen on iron during experiments with nitric

acid is due to such compounds.

6. Dissolution of Iron in Organic and Carbonic Acids

Of the organic acids (19'). oxallic, formic, citric

and acetic attack iron severely but not as readily as the

mineral acids do. Carbonic acid attacks iron almost in

the same way as any mineral acid by increasing the possibility

of corrosion through hydrogen depolarization.

7. Corrosion of Iron in Hydrochloric Acid

The first study on the dissolution of iron in

hydrochloric acid was made by Conroy (23) who immersed iron

sheets (2t? inch x 1§ inch) in appropriate solutions. He

studied the effects of acid concentration and temperature

on the dissolution rates. The loss of weight was deter­

mined at one hour intervals, but the rate of corrosion was

evaluated from hydrogen gas evolution. He concluded that:

a. The rate of dissolution was doubled for each

addition of 30 grams hydrochloric acid per litre of the

solution.

b. The rate of dissolution was doubled for each

rise of 10°C in the temperature.

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 11

Morris et al (2^) made a study of the

dissolution rates of pure iron in four concentrations (0.01 N,

0.025 N, 0.0^ N and 0.05 N) of hydrochloric acid by rotating

iron samples at 2000 rpm at 25°C with increasing amounts of

potassium nitrate (Molarity of KNO^ 0 to 0.15) and hydrogen

peroxide (Molarity of H2O2 0 to 0.16). Cylinders of the

purest iron available were rotated in 250 c.c. of corroding

solutions. The results were plotted as miligrams of iron

dissolved versus molarity of the depolarizer. The initial

dissolution rates were nearly linear with peroxide concen­

tration over the molarity range 0 to 0.08 and the maxima

were not as high as with nitrate at all four acid concen- ■

trations. With further increase in peroxide concentrations,

the rate decreased at higher acid concentrations.

The dissolution rate of pure iron in air-

free hydrochloric acid was studied by Makrides et al (25).

Polished cylindrical coupons (2.5 cm x 1.9 cm) were rotated

at'2l80r.pjn. in 400 c.c. of solution. It was shown that the

rate of dissolution of iron in air-free hydrochloric acid

was a linear function of hydrochloric acid activity for

activities between 1 and 10. The potential of dissolving

iron was a logarithmic function of hydrochloric acid activity,

They found that the dissolution rate in air-free 2 N hydro­

chloric acid was independent of stirring speed.

A study of mild steel behaviour was also

made in air-free hydrochloric acid and it was found that

the potential of mild steel in acid solutions containing

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 12

depolarizers was a linear function of the logarithm of the

solution rate.

8. Oxidation of Ferrous Ions

Rigg et al (26) investigated the kinetics of

oxidation of ferrous ions by hydrogen peroxide in sulphuric

acid. Sobkowski (27) made the same study in perchloric,

sulphuric and phosphoric acids.

Rigg and co-workers found the value of the rate

constant for the reaction between hydrogen peroxide and

ferrous ions by direct spectrometri'c observations of the

ferric salt produced (at X = 30^ ran). They confirmed that

the rate was independent of acidity (0.05 N - 0 . 8 N H^SO/j.)

and that the reaction was bimolecular over a wide range of

reactant concentrations. The concentrations of HgOg and

ferrous salts were varied from 1:25 and 1:20 respectively.

The rate constant over the temperature range 15° to *J-0°C

could be represented by the equation

k = 1.05 x lO^exp(— ) moles"1sec_1litre

RT

Sobkowski found the rate constants for the

reaction between ferrous ions and hydrogen peroxide in

perchloric, sulphuric and phosphoric acids. These constants

were measured at different temperatures and he concluded

that the rate of reaction between ferrous ions and hydrogen

peroxide was highest in the presence of phosphoric acid and

lowest in perchloric acid solutions.

A study of the rapid autoxidation of ferrous ions

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 in concentrated hydrochloric acid has been reported by

Posner (28). He found that the reaction was first-order

with respect to ferrous ion and oxygen but a more complex

function of hydrochloric acid concentration. He showed that

autoxidation occurs via a complex formed between associated

hydrochloric acid and ferrous ions. The mechanism suggested

was essentially similar to the modified Haber-Weiss (29)

formulation:

Fe++ + H+ + 02 — > Fe+++ + H02

H02 + Fe++ K5 n, Fe+++ + H02"

H+ + H02“ ^ H202

Fe++ + H 202 K6 ^ Fe+++ + OH + 0H“

Fe++ + OH K 7 ^ Fe+++ + 0H~

It was suggested by Weiss that the reason for

the slow autoxidation of ferrous ions in dilute (<4- N) acid

solution is that the primary step is the formation of 02

Fe++ + 02 02- + Fe+++ (2.1)

A F for this reaction is +30 kcal/mole. This

indicates that the equilibrium is well over tothe left

and the forward reaction is very slow. The next step in the

Weiss reaction mechanism is

H+ + 02" ^ H02

AF = -10 kcal/mole.

+
This shows that the H ion should constitute an

actual part of the active complex formed in the first step,

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 Ik

otherwise the reversal of (2.1) is more likely to occur

than the forward reaction.

The development of the Haber-VJeiss theory leads

to an expression

d (Fe~1"t~+ ) _ 'tit! [ Fe++] [ 0? ] [ f e++ ] [ H+]

® K2 [Fe+ + ] j^H+ j + k 1f H02 T Fe + + + 1

It was shown by Posner that Fe+++ in hydrochloric

acid solution is strongly complexed. It was thought that

Fe++ ions could also form a complex with hydrochloric acid

and attack of oxygen on this complex could be represented

as folloi'Ts:

(Fe++.HC.l complex) + 02 > H02 + Fe+++ + C 1 “

If the hydrochloric acid is completely dissociated

this complex formation may be expressed by the equilibrium.

H+ + Cl~ + Fe++ HFe++Cl,

and hence the autoxidation rate should be proportional to

[ H + ][C1-]

This would indicate that the reaction should •

proceed at all acid concentrations but Posner found that

the reaction occurred at a measurable rate only at hydro­

chloric acid concentration above k N„. As a result Posner

concluded that a new reactive species, capable of promoting

the autoxidation, is formed in solutions more concentrated

than k N.. It was thought that this species could be associa­

ted hydrochloric acid.

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 The oxygen attack on this complex, could be

represented by

HFe++Cl + 02 Fe+++ + Cl" + H02

and the extent of complex formation could be governed by

the equilibrium

HClass ■+ Fe++ HFe++Cl

with

George (30) studied the kinetics of the oxidation

of ferrous ions by molecular oxygen in perchloric acid

solutions as a function of pH over the temperature range

25 - *i-0oC.

In phosphoric acid solutions Cher and Davidson (31)

found that the oxidation of ferrous ions was first order

in ferrous ion.

9. Colorimetric Method of Analysis of Iron

There are many methods by which the analysis of

iron can be done colorimetrically.

Bipyridine has been used because ferrous iron

forms ared complex with 2, 2_ bipyridine at pH This

can be estimated at 520 m m (32,33). The main disadvantage

of this reagent is that the minimum concentration of ferrous

iron must be of the order of 0.02 - 0.2^- miligrams per 100 ml.

Walden et al (3*0 used 0- phenanthroline for

analysis of iron. An orange complex of the form

[(012 H8 N 2 )3 P e l x 2 is formed when ferrous ion and the

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 16

reagent react, but the resulting colour takes about 15

minutes to become stable.

A mention of the other colorimetric methods based

on iron complex formation is made here.

(1) Koling et al (35) used a, a -Bipyridyl for

analysis of ferrous and ferric iron.

(2) Gregory (36) Mehlig (37) and Scott (38) used

salicylic acid for the determination of ferric iron.

(3) Ferrous and ferric iron by sulfosalicylic

acid (39).

(4) Ferric iron by ferron (40).

(5) Ferrous iron by nitroso R-salt (41).

(6 ) Ferric iron by 8 hydroxyquinoline (42).

Snell and Snell (43) have made an exhaustive

study of colorimetric determinations of metals.

The yellow colour of ferric chloride in

hydrochloric acid has been adopted by many authors (44, 45.

46, 47).

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 CHAPTER III

THEORY

In spite of the vast amount of work that has been

devoted to corrosion studies it is not yet possible to

predict or control the behaviour of metals in corroding

media. Part of the problem is due to the lack of appreci­

ation of the various steps that are involved in the over­

all corrosion process.

An attempt will be made here to develop a plausible

and consistent scheme for the dissolution of metals in

general and iron in particular. Future researchers may be

stimulated to establish the validity of some of the contro­

versial steps in this proposal. It is felt that a thorough

knowledge of the individual processes is necessary before

effective corrosion control may be established.

A. Under Anaerobic Conditions

The dissolution of iron in non-oxidizing media, such as

hydrochloric acid, can be discussed in terms of

++
1. An anodic reaction Fe --- ^ Fe + 2e” (3»1)

2. A cathodic reaction H+ + e” --- ^ H (3*2)

3. A combination of hydrogen atoms with liberation of

hydrogen gas H + H --- ^ H 2 (3*3)

Equations (3*1)» (3*2) and (3*3) represent the

17

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 18

net result of several consecutive steps, anyone of which

may be very slow and,as a result, rate determining. In

order to have some real appreciation of these steps, one

should consider the condition of the metal surface exposed

to the corroding solution.

Metal specimens in corrosion studies are

generally polished to an arithmetic average surface rough­

ness of 20 - 30 microinches. Visual observations suggest

a mirror-smoothness of the type, shown in figure 3-1.

FIGURE 3-1. VISUAL REPRESENTATION OF POLISHED SURFACE

A microscopic study confirms the presence of hills

and valleys as shown in figure 3-2.

FIGURE 3-2. MICROSCOPIC REPRESENTATION OF POLISHED SURFACE

It will be desirable to say something about the

initiation of corrosion when the metal is put into the

solution. Figure 3-3 shows a model of the polished surface

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 19

on an atomic scale assuming a cubic crystal structure for

illustrative purposes only.

M* M*
i i

Ho M M
i ?o t

■M - M -- M -- M - M - M -• M -■ M - M
i i i
t i
M M M M - M - M -■ M - M - M

FIGURE 3-3. CUBIC CRYSTAL STRUCTURE ON ATOMIC SCALE

Atoms M# and M0 are the .potentially active sites

on the metal surface because they have unsaturated binding

energies. If there is any tendency of the matrix to

dissolve, these atoms should be the first to leave the

structure. Corrosion on iron starts at isolated points (if8)

and from some of these the attack extends as circles, streaks

or arch shaped areas. Not all the points where corrosion

is observed to start, however, suffer continued attack.

The dissolution process can now be divided into

the following elementary stages:

a. Transfer of hydrogen ions from the bulk of

the corroding solution to the iron-solution interface to

replace those liberated by reaction (3.2)

Hb+ Hi—> Hi+ (3.if)

b. Adsorption of hydrogen ions on the active

sites on the iron surface by chemisorption or physical

adsorption. Atoms such as M* shown in figure 3-3 ®ay represent

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 the active sites for this adsorption because they can be

easily reached by hydrogen ions

J
*?eS + H l+ * F* - H s+ <3-5)

c. Discharge of adsorbed hydrogen ions by one

of the two possible processes

(i)
Fe - H s+ + Fe - H s+ Fe++- H s + Fe - H (3.6)
■» # . * " *

(ii)
Fe - H * + Fe - H + + Fe Fes+ + Fe - H„ + Fe - H
* s * s Q / o s * s * s

(3.7)
Step (i) represents electron transfer

from the original active sites on which adsorption occurs,

while step (ii) represents electron transfer from a

neighbouring vacant active site.

Step (c) is more likely to occur than

the formation of ferric ions because the formation of ions

of lower oxidation state requires less energy.

d. Combination of hydrogen atoms to form hydrogen

molecules by migration of atoms from site to site

Fe - H„ + Fe - H > Fe + Fe - H ?c, (3.8)

* s # s * *

e. Desorption of ferrous ions from the surface

Fe - Feg+ Fes + Fei++ (3.9)

f. Diffusion of ferrous ions from the interface

into the bulk of the corroding solution

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 21

++ ++
Fe* — ^ Feb (3 .10)
* *

g. Removal of hydrogen molecules from the surface

by one or more of the folloiying possibilities.

(i) Solution of hydrogen gas in the fluid

at the metal-solution interface

Fe - H2s — ^ Fe + H2 dissolved (3 .11)

(ii) Absorption of hydrogen gas by the

metal matrix

Fe - H 2s Fe - H2 absorbed (3.12)

(iii) Formation of hydrogen gas bubbles on

the surface

Fe - H2 s + Fe - Hgg Fe - (H2 )n + Fe (3.13)

(iv) Removal of hydrogen bubbles by

separation from the surface

Fe - (H2 )n Fe + H2 gas (3-1*0

Small amounts of ferric ion may be

found even under anaerobic conditions. Their presence could

be result of the following set of reactions:

h. Formation of ferric ions on the surface by

disproportionation:

Fes - Fe++ + Fes - Fe++ + Fes - Fe++ ^ Fes - Fe + F%-.Fe+++

+ F e s - F e +++. (3.15)

(i) Appearance of these ferric ions at the

interface and then in the solution:

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 22

Fes - F % ++ 2-> Fes + Fej.+++ (3.16)

Feit + + £ % Fe„+++ (3.1?)

There is some evidence of autocatalysis

even in completely oxygen free corroding solutions at higher

acid concentrations ( > 5 N),.

It was suggested by Posner (28) that

there is some associated hydrochloric acid at concentrations

greater than 5 N. Therefore to provide an explanation for

the autocatalysis, it would not be unreasonable to assume

that associated hydrochloric acid molecules are also adsorbed

on the metal surface.

F % + HC1 Fe,HCl (3.18)

* *16 *

Formation of ferric ions can possibly occur

by an electron transfer reaction on the surface

+++
Fe + FeHCl + FeHOl + FeHCl- *12} Fe<,+++ + FeH„ + FeH_+
o * s ^ * s
“ / o
'o'3s * s “ * s
FeH + 3C1“ (3-19)
* s

FeJ++ Si2-> P e 1+++ (3.16)

®• Aerated Solutions

In the case of aerated acids, corrosion of iron

takes place by the two processes (16):

1. Corrosion by hydrogen gas evolution as described

previously and

2. Corrosion by oxygen depolarization

Oxygen is a very energetic cathodic depolarizer.

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 23

It is natural, therefore, that with an increase of oxygen

concentration in the electrolyte there should be an increase

in the rate of corrosion of metals, particularly iron. Iron

is an easily passivated metal,but in the presence of chloride

ions, the passivity of iron is not observed (19). Therefore

higher oxygen concentration in solution should correspond

to increasing rates of corrosion.

When oxygen is introduced into the solution,the

increase in corrosion can be considered in terms of the

following elementary steps:

a. Transport of oxygen from the bulk of the

solution to the iron-solution interface

o 2b * 1 % o 2i (3.20)

b. Adsorption of oxygen on the metal surface by

one of the two possible processes

kl9
Fes + 02 Fe -0 2s (3.21)
1 k 2o
k21.
Feg + Fes + 02 . Fe -0 S + Fe - 0 S (3*22)
1 *22
c. Surface reaction between adsorbed species

Fe - H s+ + Fe - 0 S Fes++ + Fe - 0HS- (3.23)

d. Removal of OH” by one of the two possible

ways

Fe - 0 H S" F % + OHf (3.210

+ *2^
Fe - 0HS + H. + Fes + H20 (3.25)

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 zk

e. Formation of ferric ions either at the inter­

face or in the hulk.

Fe++ + H+ ( + 0.,. , . Fe+++X + HO? (3.26)

(i-b) (i-b) 2(i-b) * Xi-b) 2

FeJ++ + H s ^22^ Fet+ + H S+ (3.2?)

P?t^) + H°2(I-b) ^ *£» + HOi(i-b) <3.28)

H0"
2 (1-b) + H U-b) ^u-*) (3'29)

Fe++
(i-b) + HoO?f,
2(i—b) „ 3 ^
K Fe+++
(._b) + OH..
(1-b) + 0H“(1_b)

°H (i-b)+ H2°2(i-b) ~ > H2 ° (i-h) + H02(i-b) (3.31)

II02(i-b) + h2°2(i-b) °2(i-b) + H2°(i-b) + 0 H (i-b) (3 32) i

2Fe*++ + Fe 3Fe*+ (3.33)

k 36

where

s is surface

b is bulk

i is interface

(i-b) is interface or bulk

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 CHAPTER IV

EXPERIMENTAL

A., Materials

1. Iron

Iron rod, supplied by Armco Steel Corporation,

Ohio, U.S.A., was machined into cylinders of 0.^7" in dia­

meter. Different lengths of cylinders varying from 0.1^8"

to 0.592" were used. The purity of the metal was 99.715$*

The analysis as given by the manufacturer is found in

Appendix I .

2. Hydrochloric Acid

Analar grade hydrochloric acid supplied by the

British Drug House Ltd. was diluted with distilled water.

3. Hydrogen Peroxide

Analar grade hydrogen peroxide was also supplied

by the British Drug House Ltd.

B. Apparatus

The cylindrical iron samples were rotated on a stainless

steel shaft. , Plexiglass sleeves and a cap screwed tightly

at the end protected the ends of the iron sample and steel

shaft from corrosion.

The samples were rotated at speeds ranging from 2000

to 12000 r.p.m. by means of a type 7HM Hoover Vacuum cleaner

177160
25

UNIVERSITY OF WINDSORLIBRARY

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 26

motor. Figure ^-1 is schematic representation of the

experimental apparatus.

The speed of the motor was regulated by a powerstat

and a constant voltage power supply. Shaft speeds were

measured by means of a type 1531-A strobotac, produced by

the General Radio Corporation.

The reaction cells consisted of specially designed

jacketted vessels fabricated from two pyrex beakers. Water

was forced through the space between the beakers by means

of a pump from a thermostated bath. A laboratory jack was

used to adjust the reaction vessels to the required height.

The reaction vessel was fitted with a $ x 5 x | inch

plexiglass plate holding three radially mounted baffles.

These baffles were designed to prevent vortex formation

when the shaft was rotated at high speeds. Three holes of

3 / V 1 diameter were bored in the plexiglass plate to provide

means of aeration, means of removing a sample from the

solution and entry of the shaft into the corroding solution.

The acid solutions were saturated with air, nitrogen

or oxygen as required. In order to minimize the loss of

hydrochloric acid, over the normal period of .corrosion, these

gases were passed through three wash bottles containing acid

of the same concentration as in the reaction vessel. All

wash bottles were kept at the same temperature as the

corroding samples.

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Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

PULLEYS

SELF ALIGNING BEARINGS

STAINLESS STEEL SHAFT

AERATION .
PLEXIGLASS SLEEVE

1500 ml BEAKER- -WATER EXIT

1000 ml BEAKER
1 OF 3 BAFFLES

METAL SAMPLE
PLEXIGLASS CAP
WATER INLET

ro
-o
FIGURE 4-1 APPARATUS ARRANGEMENT
 28

C. Procedure

A measured volume of hydrochloric acid solution in the

reaction vessel was flushed with the appropriate gas for

about 20 - 30 minutes before each corrosion run.

The machined specimens were manually polished with

180, 2*4-0, 320, *400 and 500 emery papers. The polished

samples were washed initially with distilled water, then

with acetone for degreasing and finally rewashed with

distilled water.

When dry, the samples were individually weighed. After

each run the samples were washed with distilled water, dried

and then re-weighed. This weighing before and after enabled

a material balance comparison to be made with the hydrogen

peroxide analytical procedure. Experiments, in which material

bgLlances differed by more than 6% were rejected.

Periodically a sample of solution was withdrawn by

means of a pipete for analysis. The concentration of iron

as (Fe+++) and total iron was determined by a photometric

method described in Appendix II.

To eliminate excessive volume change during the corrosion

period, an equal volume of fresh acid was added to the reaction

vessel for every sample of solution withdrawn for analysis.

Throughout the corrosion period, the flow of gas, ro­

tational speed and temperature were kept constant.

The surface roughness of the samples was measured before

and after each run by means of a Profilometer supplied by

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 29

Micrometrical Manufacturing Company of Ann Arbor, Michigan,

U.S.A.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 CHAPTER V

RESULTS AND DISCUSSION

A. General Corrosion Behaviour of Iron

Both oxidation states of iron are found in corroding

solutions of hydrochloric acid over the concentration range

(3 to 5.37 N). The proportion of ferrous ion is much greater

at the lower acid concentrations. The relative proportions

of ferrous and ferric ion depend upon the acid concentration

and on the gas with which the acid is saturated. The relative

amount of ferric ion increases while that of ferrous de­

creases with increasing oxygen and acid concentrations. The

effect of acid concentration is so pronounced that even in

oxygen free solutions, there appears to be some ferric ion

present if the concentration is greater than 5 N.

The relative ferric ion concentrations under different

conditions are shorn in figure 5-1.

B• Dissolution of Iron In Oxygen-free Solutions

1. Order of Reaction

The first point is to establish the order of

dissolution of iron under anaerobic conditions. Corrosion

of iron in nitrogen saturated solutions is due, simply, to

the evolution of hydrogen gas, therefore it will be easiest

to consider the dissolution in oxygen-free solutions. Most

30

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 31

7 4500 R.P.M.
500 ml. volume
2.84 sq. cm.

5
-p

L_

0
0 1 2 5
TIME, Hours

FIGURE 5-1 COMPARISON OF FERRIC IRON CONCENTRATIONS

UNDER DIFFERENT CONDITIONS

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 32

of the. present work has been carried out at *1-500 r.p.m.

in *{-.027 N hydrochloric acid with exploratory experiments

having been done in 3.027 N and 5.37 N hydrochloric acid

solutions.

Analytical studies during corrosion show that most

of the iron in solution is in the ferrous state but sub­

stantial quantities of ferric ions have been found also.

The presence of ferric ions could be due to the dispro-

portionation.

3Fe++ ?===> 2Fe+++ + Fe (5.1)

itfhlch has been considered to be a surface phenomenon

according to equation (3.15). It must be emphasized that

there is never an equilibrium relationship between the

ferric and ferrous ion concentrations in solution.

The rate of formation of ferric ions in solution

is about 3 - of the ferrous ion rate. The slight variation

of ferric ion concentration with temperature and surface

area shows that their presence cannot be related to experi­

mental conditions very readily. It is not unreasonable to

suspect that a small amount of oxygen from the atmosphere

could leak into the solution and be responsible for the

presence of- ferric ions.

Figure 5-2 shows some typical data for the

dissolution of iron in oxygen-free solutions of hydrochloric

acid over a fairly wide range of temperatures. Plots of

total iron concentrations versus time are always linear,

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 33

lk
k500 R.P.M.
500 ml. volume
2.8V sq. cm.

12
x 10 » Moles/litre

10

8
Concentration

6
Iron

0
0 1 2 3 5 6
TIME, Hours

FIGURE 5-2 RATE OF DISSOLUTION OF IRON IN AIR-FREE HC1

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 3^

for acid concentrations below 6 N. At low acid concentra­

tions the rate of dissolution of iron can be written as

ft (Fe) =

where kQI the rate constant, is a function of temperature,

area and possibly of rotational speed.

When this study was extended to higher acid

concentrations (>5-37 N), it was found that the dissolution

rate was a function of time. Plots of total iron concentra­

tion versus time become curved as shown in figure 5-2, This

curvature implies autocatalytic dissolution under oxygen-

free conditions.

A possible explanation for this autocatalytic

phenomenon could be considered in terms of the work of

Posner (28) who suggested that associated hydrochloric acid

molecules could play a significant role at higher acid con­

centrations. It would be reasonable to assume that some

associated hydrochloric acid molecules are adsorbed on the

metal surface with subsequent formation of ferric ions by

an electron transfer reaction on the surface according to

Fe + FeHCls + FeHCls + FeHCLs Fes + FeHg + FeHs

+ FeHs + 3C1” (3.19)

Ferric ions formed by (3.19) could then take part

in. reaction (5.1) to produce ferrous ions to give an indi­

cation of autocatalysis during corrosion at higher acid

concentrations with nitrogen as the saturating gas. In the

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 35

present study it is not possible to justify fully the

above explanations. Further work must be done before

dissolution at higher acid concentrations can be completely

appreciated.

2. Effect of Temperature and Rotational Speed on the

Dissolution Rate

The effect of temperature on the dissolution rate of

iron under anaerobic conditions was studied over the tempera­

ture range 26° - 45°C. Figure 5-3 shows the data from runs

made in 4.027 N hydrochloric acid. ' The Arhenius activation

energy is of the order of 9.4 kcals per gram mole.

The high value of the activation energy suggests

that the controlling step in the dissolution of iron under

anaerobic conditions may be a chemical process rather than a

physical one at lower acid concentrations.

A few exploratory runs were made in.3.04 N hydro­

chloric acid to determine whether variation of rotational

speed would have any effect on the corrosion rate. Table 5-1

shows that for the range 3300 - 6500 r.p.m. the dissolution rate

is essentially constant. This behaviour confirms the suspicion

that the controlling step in the dissolution of iron in

oxygen free hydrochloric acid solutions of low concentration

is a chemical process.

TABLE 5-1

EFFECT OF ROTATIONAL SPEED ON THE DISSOLUTION RATE

R.P.M. RATE CONSTANT X 10^

3300 0.35

6500 0.34

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 36

4500 R.P.M.
500 ml. volume
2.84 sq. cm.

10

11
3.0 3.1 3.2 3.3 3.5

| x lo3

FIGURE 5-3 ARRHENIUS PLOT FOR 4.027 N HC1

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 37

3. Effect of Superficial Surface Area on the Dissolution

hfef ;
----- ~

The effect of superficial surface area was studied

in ^.027 N hydrochloric acid at 35°C in nitrogen saturated

solutions. Figure 5-^A suggests that there must be some

relationship between the zero order rate constant and the

apparent surface area of the specimen.

Figure 5-^B shows that the zero.order rate constant

is proportional to three quarter power of area. This

dependance on area may be characteristic of metals which

can displace hydrogen gas from acid solutions. This behaviour

has been confirmed by Bodner (8) who found the rate of

dissolution of titanium to be proportional to the three

quarter power of area.

The three quarter power-area dependance could be

explained possibly in terms of the molecular hydrogen

formation on the surface of the corroding sample. Atomic

hydrogen in forming a molecule would require a surface on

wiiich to unite and this could cause blocking of the surface

available for corrosion. The mechanism of hydrogen formation

is clear from the equations:

Anodic reaction Fe --- ^ Fe + 2e

Cathodic reaction 2H+ + 2e" ----- 2(H) _— ^ H2

Nascent
k. Empirical Equation

The results indicate that corrosion under anaerobic

conditions occurs only by the evolution of hydrogen gas.

The dissolution of iron under anaerobic conditions could

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 38

ps
0
Si 4500 R.P.M.
1 8
<D 500 ml. volume
•P 4.027 N HC1
•H 35°C
r-H 6
\
10
0)
i—t
o
a
vo
o 2
K
O 0
JO
0 1 2 3 6
AREA, sq. cm.

FIGURE 5-4A EFFECT OF SUPERFICIAL AREA UNDER

ANAEROBIC CONDITIONS

U
3
0
si 4500 R.P.M.
1
0) 8 500 ml. volume
fH 4.027 N HC1
•P
35°C
6
W
<U
rH
o
a
VO
o
2

o 0
JO
0 1 2 6
(AREA)3/Z\ (sq. cm.)3^

FIGURE 5-4B EFFECT OF SUPERFICIAL AREA UNDER

ANAEROBIC CONDITIONS

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 39

"be discussed in terms of the following basic processes:

Fe* - H s+ + Fe* - H s+ J ^ > Fe*++H s + Fe* - H g (3 .6 )

or Fe* - H s+ + Fe* - H g+ + Fe0 Fe0++ + Fe* - H s

+ Fe* - H s (3.7)

3Fe++ 2Fe+++ + Fe (3.15)

In essence, the dissolution of iron in hydrochloric

acid is in the form of ferrous iron with only a small

quantity of ferric ions being generated.,

The results of these experiments can be summarised

by the following empirical equation

dl|el sa Ki (exp (_ 2 ^ 0 ))(r .p .M#)O(h c 1) (5.2)

where d(Fe) = rate of formation of total iron species in

dt solution expressed in moles/litre-hour
O
A *= superficial surface area, cm

V = volume of corroding solution, litres

The average value of has been found to be 13.1.

Therefore equation (5.2) can be written tentatively as

= 13<1 Ul2^(exp (- 2|2°))(r .p .M.)°(HC1) (5.3)

Equation (5*3) is a valid correlation of experi­

mental data over the range of conditions

1) Temperature : 26-^5°G

2) Volume. : 400-600 ml.

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 40

3) Area : 1.43 - 5*72 cm2

4) Hydrochloric Acid Concentration: 3*04 - 4.027 N HC1

5) Time upto : 6 hours

6 ) Rotational Speeds : 3300 - 6500 R.P.M.

On the basis of the work of Makrides (25) and

figure 5-5 . this equation may not be too unreasonable for

tiie concentration range 0 < ( H C 1 ) < 4 N . It must be empha­

sized that this is a good approximation for the present.

More work is needed to establish the complete validity of

this relationship.

C. Dissolution of Iron in Air and Oxygen Saturated Solutions

1• Colour of the Iron Solutions During Dissolution

All corroding solutions were colourless before

any corrosion occured. After the iron specimen was immersed

in the solution, yellow colour started appearing under air

and oxygen saturation. This yellow colour is an indication

of ferric ions.

In the case of nitrogen saturation, the solutions

were almost colourless indicating that there was hardly

any ferric ion present.

The colour intensity of ferric chloride increased

with the concentration of the acid as well as with the

amount of iron in the solution.

2. Order of Reaction

To find the order of reaction corrosion studies were

made both in air and oxygen saturated solutions. Most of

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 4-1

7
. 4500 R.P.M.
2.84 sq. cm.
500 ml. volume
35°c
.6

.5
Moles/litre-hour

.3

.1

0 1 2 3 5
NORMALITY OF HYDROCHLORIC ACID

FIGURE 5-5 EFFECT OF ACID CONCENTRATION UNDER

ANAEROBIC CONDITIONS

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 42

the present work has been carried out at 4500 r.p.m. in

3.04 N and 4.027 N hydrochloric acid with exploratory experi­

ments having been done in 6.04 N hydrochloric acid solutions.

Analytical studies show the presence of both

ferrous and ferric ions in the corroding solutions. The

relative proportions of ferrous and ferric ions depend

upon the acid concentration and on the gas with which the

acid is saturated.

As shown in figure 5-6, plots of total iron

concentration versus time are always curved. This curvature

is essentially an evidence of autocatalytic behaviour. The

increase in surface area produced by increasing surface

roughness during the course of corrosion is not. responsible

for this curvature. Substitution of four freshly polished

iron specimens during the course of a normal 5 - 6 hour

corrosion period had no effect on the curvature as shown

in figure 5-7 *

The rate of dissolution of iron in solutions

containing oxygen can be written as

-dr1 = <Fe)”

where Fe is total iron concentration in the corroding

solution. Taking logs on both sides yields

log (Fe) = log kn + n log (Fe)

dt

where kn ,the rate constant, is a function of temperature,

surface area, acid concentration and possibly of rotational

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 28
^500 R.P.M.
2.8 sq. cm.
500 ml. volume

2*4-

20
, Moles/litre

16
x 10

12
ConcentrationI

8
Iron

3.02 N
30°c
Air

0
0 1 2 3 4 5 6

TIME, Hours

FIGURE 5-6 RATE OF DISSOLUTION OF IRON UNDER AERATED

CONDITIONS

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 44

7
4-500 R.P.M.
500 ml. volume
3.02 N HC1
35°c
Air
6

5
x 10 , Moles/litre

3
Concentration

2
Iron

SPECIMEN 1 SPECIMEN 2 SPECIMEN 3 SPECIMEN 4-

0
0 1 2 3 5 6
TIME, Hours

FIGURE 5-7 EFFECT OF FRESH SURFACE SUBSTITUTION

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 speed and n Is the order of reaction.

A plot of log SL_ (Fe) versus log (Fe) showed the

dt
value of n to be in the range 0.4<n<0.6. By the method of

trial and error the most appropriate value of n seems to

be 0.5 because this value gives the best linear relation­

ship for the total iron versus time plots.

A plot of (Fe)2 versus time for a wide range of

conditions gives a linear relationship as shown in figure

5-8. This indicates that there must be half order dependance

on total iron concentration during the corrosion.

All of the plots in figure 5-8 show an ordinate

which is somewhat variable, implying some iron concentrat­

ion at zero time. All of the data given have been determined

in apparatus which was cleaned and rinsed in the normal

way. Previous researchers (50) have shorn that considerable

metal may be adsorbed on the glass surface. Part.,of the

iron concentration at zero time can be explained in terms

of the attack of acid vapors on the specimen surface over

a 5 minute period during which the shaft was brought to

constant rotational speed with the specimen just above the

corroding solution.

3. Reproducibility

In order to check the reproducibility, duplicate

runs were made and some were made three times. A typical

plot of a duplicate run is shown in figure 5-9. Gas flow

rate, temperature and speed were kept constant in all the

cases.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 46

7
4500 R.P.M.
2.8 sq. cm.
500 ml. volume

0
o
g
VPl
5
o
I— 1
<D
F<
-P
•H
iH
\
CO
<D
H
O
g

vr\
*
0
1-- 3
-3-
o
t-l

H
£
O
•H OC.
■p 2
ctf
Ft
-p
£
<D
O
£
o
o 1
£
o
u
M

0
0 1 2 3 5 6

TIME, Hours

FIGURE 5-8 HALF ORDER PLOTS UNDER AERATED CONDITIONS

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 47

28
5800 R.P.M.
2.54- sq. cm.
500 ml. volume
5.37 N HC1
Air
2k
, Moles/litre

20

16
x 10
Concentration

12

8
Iron

e Run A
o Run B

0
2 3
TIME, Hours

FIGURE 5-9 REPRODUCIBILITY

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 48

4. Effect of Rotational Speed on the Dissolution Rate

The effect of rotational speed on the dissolution

rate was studied in 4.027 N and 6.04 N hydrochloric acid

at 35°C in air saturated solutions at speeds ranging from

0 to 11000 r.p.m. Figure 5-10 illustrates the dependance

of velocity constant on rotational speed. It will be noted

that at the higher acid concentration the corrosion rate

decreases with increasing velocity initially, passes through

a minimum and then increases. A similar phenomenon was

observed by Whitman and Russel (17) who studied the corrosion

of iron cylinders in sulphuric acid. They found that the

corrosion of stationary samples depended on the acidity,

but it is significant that the corrosion rate was indepen­

dent of acid concentration at 4000 r.p.m.

Their results could be explained on the basis

that corrosion in air saturated solutions proceeds by two

processes. The first is "corrosion by hydrogen gas. evolution"

and the second is "corrosion by oxygen depolarization".

The decrease of corrosion with increase of speed

has been explained by Maclnnes' work (49) in terms of over­

voltage variation. Corrosion of stationary samples is pri­

marily determined by the rate of hydrogen gas evolution,

particularly with the concentrated acids. The effect of

sample velocity is to decrease the size of hydrogen bubbles

thus increasing the work required to form smaller gas

bubbles. Velocity increases corrosion by oxygen depolari­

zation, 'since it thins down the effective film through which

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 1*9

500 ml, volume

Air

.0

u .6
o
vn
o
0) .2
u
•p
•H
H
\
n
<D
r— I
O
S 8
If.027 N, 2.8^f sq. cm

0
2000 6000 8000 10000

R.P.M.

FIGURE 5-10 EFFECT OF ROTATIONAL SPEED

ON DISSOLUTION RATE

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 50

oxygen must diffuse.

The corrosion, being the sum of two effects,

will be determined mainly by the hydrogen gas evolution at

low velocities and by oxygen depolarization at high veloci­

ties and should consequently pass through the minimum point

in the intermediate range.

In the present study it has been shown that the

rate of corrosion decreases with increase of speed in the

initial stages and then increases to a constant value for

speeds higher than 4500 r.p.m. To avoid damage to the

experimental equipment a rotational speed of 4500 r.p.m.

was chosen for most of the research work.

At lower acid concentrations the corrosion rate

is independent of rotational speed. This suggests that

oxygen depolarization plays a predominant role.

5. Effect of Temperature on Dissolution Rate

The effect of temperature on the dissolution ..

rate of iron was studied over the range 26° - 45°C under

oxygen and air saturation. Figure 5 - H shows the data from

runs made in 4.027 N hydrochloric acid. The Arhenius

activation energy is of the order of 9.4 .kcal's per gram

mole. Similar results were obtained for other acid concen­

trations .

The high value of activation energy and negli­

gible effect of rotational speed after 4500 r.p.m. indicates

that the controlling step in the dissolution of iron is a

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 •51

Air

3.0 3.1 3.2 3.3 3.5

1 x lo3

FIGURE 5-11 EFFECT OF TEMPERATURE

ON DISSOLUTION RATE

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 chemical process rather than a physical one.

6. Effect of Hydrochloric Acid Concentration on the

t)issolu tion~RaTe~

The effect of acid concentration under air-

saturation was studied over the range 3.04 - 6.04 N hydro­

chloric acid. A plot of the half order rate constant

versus acid concentration as shown in figure 5-12 gives

a linear relationship for moderately concentrated acids

(up to 5 N) but at higher concentrations the rate becomes

a more complex function of acid concentration.

This behaviour is explained by Posner (28) by

assuming that there is a complex formed between ferrous

ion and hydrochloric acid as described previously in the

Literature Review.

In the present study it is not possible to write

the rate expression for higher acid concentrations. Further

work must be done before it can be completely appreciated.

7* Effect of Superficial Surface Area on the

Dissolution Ra€e

The effect of area was studied in 4.027 N

hydrochloric acid at 35°C in air saturated solutions.

Figure 5-13A shows the half order rate to be a linear

function of the apparent surface area. This plot implies

that there is a finite half order rate with zero surface.

From this apparent contradiction it appears that the

corrosion rate cannot be directly proportional to super­

ficial surface area.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 53

Jj-500 R.P.M.
500 ml. volume
2.8^ sq. cm.
Air

vH
1
u
2
o
£

o
fl>
u
-p
•H
i-l
CO
o
rH
O
S

o
T~i

h!

//
t/,
1

1 2 4-
NORMALITY OF HYDROCHLORIC ACID

FIGURE 5-12 EFFECT OF ACID CONCENTRATION UNDER

AERATED CONDITIONS

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 5^

4500 R.P.M.
500 m l . volume
4.027 N HC1
35°G
Air

T—I

•H

0 1 2 3 4 5

AREA, sq. cm.

FIGURE 5-13A EFFECT OF AREA UNDER AERATED CONDITIONS

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 Figure 5-13B shows that the half order rate is

proportional to the three quarter power of the area. This

may be the characteristic of metals which can displace

hydrogen gas from acid solutions. This has been confirmed

by Lui (6) and Bodner (8), who found the rates of dissolu­

tion of tin and titanium to be proportional to the sqare

root and three quarter power of areas respectively. The

rate of dissolution of copper (1,4) has been found to be

directly proportional to the surface area in acid solutions

Copper does not displace hydrogen from acid solutions.

8. Effect of Volume on Dissolution Rate

The effect of solution volume was studied in

6.04 N hydrochloric acid at 40°C in air-saturated solutions

by rotating the iron samples in 400, 500 and 600 ml. of

corroding fluid. Plots of iron concentration in moles

per litre versus time have been shown in figure 5*-14 for

the three volumes. Figure 5-15 shows the moles of iron

dissolved as a function of time. It becomes clear that

the rate of corrosion in moles per litre per hour is

inversely proportional to the volume of corroding solution.

9. Effect of Oxygen on Dissolution Rate

The effect of oxygen on the dissolution rate

was determined by bubbling nitrogen, air and oxygen through

the solution keeping the rate of the gas constant (about

1.5 litres/min.). Figure 5-15 indicates that the rates of

dissolution are most effectively correlated in terms of the

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 56

4500 R.P.M.
500 ml, volume
4.027 N HC1
35°c
Air
2

0
1
u
2
o
.c
•
o
8
o
u
■p

CO
<D
i—I
o .6
s

o
tH

ri|Oi
M

0 1 2 3 5
(AREA)"^1, (sq. c m . ) ^ ^

FIGURE 5-13B EFFECT OF AREA UNDER AERATED CONDITIONS

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 57

2.8

500 ml
24

0)
Si
-p
•H
i— I
\
CO
O
tH
O
a 600 ml
-4-"
o
tH 16
X

O
•H
■P
OS
Si 12
-P
Si
fl)
o
si
o
o
si
o 8
Si
M

0 1 2 5

TIME, Hours

FIGURE 5-14 EFFECT OF VOLUME ON DISSOLUTION RATE

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 58

1^-

12

to 10
<o
H
O
a
-3-
o
8

•P
a
pi
o • 400 ml
O 500 ml
a ■ 600 ml
o

0
0 1 2

TIME,. Hours

FIGURE 5-15 EFFECT OF VOLUME ON DISSOLUTION RATE

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 59

28

4500 R.P.M.
500 ml. volume
2.84- sq. cm.
027 N HC1
2k

20
hour”

16
(Moles/litre)

35 Q
12
lO^,

0
0 0.2 0.6 0.8 1.0
(PARTIAL PRESSURE OP OXYGEN IN ENTERING GAS)0 *5 ,
(Atm.)9•5

FIGURE 5-16 EFFECT OF OXYGEN ON DISSOLUTION RATE

UNIVERSITY OF WINDSOR LIBRARY

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 60

square root of the oxygen partial pressure in the gas phase

with which the solution is equilibrated.

A detailed study of the oxygen-effect was made in

4.027 N hydrochloric acid over the temperature range of

26° - 45°C. Table 5-2 shows the typical values of rate

constants.

.......... 5-T

EFFECT OF OXYGEN

4500 r.p.m.
2.84 sq. cm.
4.02? NHC1 '

Temperature Type of Aeration Rate Constant x 10^

°C (moles/litre)® •■5hr“ ^

45 °2 198

45 Air 87.0
#
45 n2 1.03
40 °2 168
40 Air 76
40 n2 0 .56*
35 °2 144.0
35 Air 62.0
35 N2 0.47*
30 o2 96
30 Air 43
*
30 N2 0.316
26 02 - 85
26 Air 35
*
26 n2 O .29
These are zero order rates with units moles/litre-hr.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 61

This half order dependance on the concentration

of oxygen implies dissociation of oxygen. This may be the

result of some process similar to that suggested by

equation 3*21.

10, Empirical Equation

The results indicate that three processes of

corrosion may be proceeding simultaneously in aerated acids.

The first process, corrosion with the evolution of hydrogen

gas, occurs alone in the runs under nitrogen and is termed

corrosion by hydrogen gas evolution. The second occurs

together with the first, in runs under air or oxygen and

is known as corrosion by oxygen depolarization. The third

is an autocatalytic contribution.

These three processes of corrosion can be

represented as follows:

Fe + 2H+ --- > Fe++ + 2H (5*5)

Fe + H+ * 02 ___ ^ Fe++ + H02" (5.6a)

Fe++ + H + + 02 -- ^ Fe+++ + H02 (5.6b)

2Fe+++ + Fe 3 Fe++ (5.7)

Reactions (5*6) and (5*7) would be responsible

for the increase in corrosion when oxygen is introduced into

the hydrochloric acid solution.

In the present work it is not possible to separate

corrosion due to oxygen depolarization from that due to

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 62

autocatalysis. Therefore the results of these experiments

can be summarized by the following empirical rate equation.

dgai „ 1 ^ 1 (HCl) exp (- ^ 2 0 ) ' [kj + V PO 2 )0-5 tFe)°.5;l(5.8)

where (Fe) is the total iron concentration in the corroding

solution expressed in moles/litre

t is the time in hours

A is the superficial area in crn^

V is the volume in litres

(HCl) is the normality of hydrochloric acid

PQ is the partial pressure of oxygen in atmospheres

T is the temperature in K°

The values of and K£ have been found to be

13.1 and 1.18 x 10^ with the detailed calculations shown in

Appendix III.

Thus equation (5.8) can be written as

dl|gl _ (A I— (HCl) exp (- 2 ^ ) ^13.1 + 1.18 xlO^ (P0 2 )°,5 (Fe)0 ^

I(5.9)

This equation (5.8) is a valid correlation of

experimantal data over the range of conditions.

1) Temperature 26° - 45°C

2) Partial Pressure of oxygen: 0 - 1 atm.

-4
3) Time up to 6 hours ( 0 < F e < 2 3 . 1 x 10 )

4-) Hydrochloric acid concentration 2.4 - 5-37 NHC1

5) Volume 400 - 600 ml.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 63

6) Area 1 A 3 - 5-72 cm2

7) Rotational speeds ^500 - 11000 R.P.M.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 CHAPTER VI

CONCLUSIONS

The corrosion of iron proceeds by three processes:

A. Corrosion due to hydrogen gas evolution

B. Corrosion due to depolarization by oxygen

C. Corrosion due to autocatalysis

Corrosion by hydrogen gas evolution is responsible for

the appearance of ferrous ions in solution. The presence

of oxygen will accelerate the dissolution. By virtue of

slow autoxidation of ferrous species, oxygenated solutions

contain both ferrous and ferric ions. The simultaneous

existence of the two oxidation states in solution makes it

difficult to separate the effect of oxygen depolarization

from that of autocatalysis.

Because the corrosion rate was independent of rotational

speed for peripheral velocities above 6700 cm/min and .the

Arhenenius activation energy was quite high, of the order

of 9.4 K cal per gram mole, it is reasonable to suggest

that the controlling step in the dissolution of iron is

chemical rather than physical for the range of conditions

studied.

The surfaces of corroded iron samples are distinctly

different from those of copper, tin and titanium (1,4,6,8).

64

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 The deep furrows suggest that the corrosion process is not

completely uniform over the cylindrical surface. Absorption

of evolved hydrogen by the metal matrix may lead to forma­

tion of high pressure gas pockets which may stress the

corroding surface.

As expected, the corrosion of iron shows an autocata-

lytic behaviour. The metals copper, titanium, tin and iron

have been subjected to fundamental studies and all show an

evidence of autocatalysis. It is possible to generalize

that any metal capable of existing in two or more oxidation

states should show an autocatalytic behaviour.

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 CHAPTER VII

SCOPE OF WORK IN FUTURE

As a result of the present investigation, the following

recommendations can be made for the f u t u r e :

A. Work should be done at lower acid concentrations where

the dissolution rates would be quite low. Under these

conditions it may be possible to separate the effects of

oxygen depolarization from that of autocatalysis.

B. Work is needed under n i t rogen saturation before the

complete validity of the present empirical equation can be

accepted.

C. Attempts should be made to measure the amount of hydro­

gen gas evolved during corrosion to confirm the suspicion

that some hydrogen is absorbed by the metal matrix when the

specimens are rotating.

D. Development of techniques to measure the concentrations

of species adsorbed on the metal surface may help in inter­

preting the experimental data theoretically. It would be

useful to test for the presence of hydrogen peroxide in

the corroding solution.

E. The corrosion study should also be extended to specimens

of different shapes and cylindrical samples of different

diameters keeping the area constant.

66

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 F. The real proof of validity of a rate equation is its

prediction of corrosion rates for other configurations of

sample and corroding fluid. It would be worthwhile to

determine how well the presently derived rate equation

will correlate the results of studies made on a system

involving a' fluid flowing through an iron pipe. Another

approach would be to flow the liquid over the walls of

a horizontal cylinder, with streamlined protective plastic

end-caps, at rates comparable to the peripheral velocities

of the present experiments.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 REFERENCES

1„ Lu, B.C.Y.,and Graydon, W.F., J. Am. Chem. Soc., 77,

6136 (1955).
2„ Lu, B.C.Y. and Graydon, W.F., Can. J. Chem., ^2, 153
(195*0.
3. Weeks, J.R. and Hills, G.R., J. Electrochem. Soc., 103,
203 (1956)

4. Gnyp, A.W., Ph. D. Thesis, Toronto, (1958).

5. Ammar, I. A. and Riad, S., J. Electrochem. Soc., 106,

926 (1959).

6 . Lui, Alex W.K., Ph. D. Thesis, Windsor, (1964).

7. Gee, E.A. and Golden, L.B., Ind. Eng. Chem., 4l, 1668
(19*19).
8. Bodner, J.J., M. A. Sc. Thesis, University of Windsor,
(196*0.
9. Schchikow, Krasil, J., ,J.Chem., (U.S.S.R.), 14,- 261,
(1944).

10. Hudson, R.M., Corrosion, 20, 245t (1964).

11. Hudson, R.M., Magor, J.K. and Stragand, G.L., J'. Amer.
Ceram. Soc., 4l, 23 (1958).

12. Podesta, J.J. and Arvia, J.J., Electrochimica Acta, 10,

159 (1965).

13. Leko, A.M., Bull, Soc. Chim., Belgrade, JL4, 249 (1944).

14.' Demon, G.H., Ind. and Eng. Chem., 67 (1941).

15. Archer, H.R. and Howlett, J ., Chemistry and Industry,

Ji, 605 (1949).
16 . Whitman, W., Russell, R., Welling, C. and Cochrane, J.,
Ind. and Eng. Chem., 672 (1923).

68

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 17. Landolt - Bernstein, 5th ed., 1104.

18. Gatos, Harry, C., J. Electrochem. Soc., 286 (1956)

19. Tomashov,- N.D.,"Theory of Corrosion and Protection of

Metals", The Macmillan Company, New York 1st edition
(1966).
20. Whitley and Hallimond, Carnegie Schol. Mem., 2* 1 (1918).

21. Vetter, K.J., Z. Electrochem,- ^6. 106 (1952).

22. Bonhoffer, K.F., Brauer, E. and Langhammer, Z. Electrochem

2£, 52 (19^8).

23. Conroy, Games, T., J. Soc. Chem. Ind., 20, 316 (1901).

24. Morris, B., Abramson and Cecil V. King., J, Am. Chem. Soc.
6 1 , 2290 (1939).

25. Makrides, A.C., Komodromos, N.M. and Hackerman,

J. Electrochem. Soc., 102, 363 (1955).

26. Rigg Tyson, Taylor Willium and Weiss Joseph, J. Chem. Phys
22, 575 (195*0 •
27. Sobkowski, Jerzy, Roczniki Chemi.Ann Soc. Chim., Polonorum
26, 1503 (1962).

28. Posner, A.M., Trans. Faraday Soc., 42, 382, 389 (1953).

29. Haber and Weiss, Proc. Roy. Soc. A., 147. 332 (1934).

30. George, P.J.,‘ Chem. Soc., (London), 4349 (1954).

31. Cher, M. and Davidson, N.J., Am. Chem. Soc., 77, 793
(1955).'

32. "Book of A.S.T.M. methods of Chemical Analysis of

Metals", 325 (1946).

33. "American Soc. for Testing Materials" (1946).

34. Walden, G.H., Jr., Hammett, Louis, P. and Chapman, Ray, P.

J. Am. Chem.* Soc., 3908 (1931).

35. Koenig, Ruth, A. and Johnson, C.R., J, Biol. Chem,, 143,

159 (1942).

3 6 . Gregory, A.W., J. Chem. Soc.: Trans. 22.* 93.(1908),

37.' Mehlig, J.P., Ind. Eng. Chem. Anal. Ed., JLO* 136 (1938).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 70

38. Scott, R.O., Analyst, 66, lip2 (194-1).

39. ' Kennard Martha and Johnson, C.R., Proc. Trans. Texas
Acad. Sol., 22, 4-5 (194-4-).

4-0. John, H. Yoe., J. Am. Chem. Soc., £4, 4-139 (1932).

4-1. Van Klooster, H.'S.', J. Am. Chem. Soc., 4^5, 74-6 (1921).

4-2," Moeller Therald, Ind. Eng. Chem., Anal. Ed., 15, 34-6
(194-3).

4-3. Snell, F.D.' and Snell, C.T., "Colorimetric Methods of

Analysis", D. Van. Nostrand Co, Inc., New York 3rd ed.
2, (1954-).

4-4-.'’ Huttner, C., Z Anorg. Chem.', 86, 34-1 (1914-).

4-5. Hostetter, J.C.', J. Am. Chem. Soc., 4l, 1531 (1919).

4 - 6 "Book of A.’S.T.M. Methods of Chemical Analysis of

Metals" (194-6).

4-7.' "American Soc. for Testing Materials", Philadelphia, Pa

(194-6).-

4-8. Evans, Ulick, R., "An Introduction to Metallic Corrosion",

Edward Arnold (Publishers) Ltd., 2nd ed. (19&3)•

4-9. Maclnnes and Contieri, J. Am. Chem. Soc., 4_1, 2013 (1919).

50. Lu, B.C.Y. and Graydon, W.P., Can. J. Chem., 22, 153 (1954-).

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX I

Typical Analysis of High Purity Research Iron

Supplied by Armco Steel Corporation, Ohio, U.S.A.

Hardness

75 (Rockwell Hardness Tester)

Analytical Results

Element Percent Method

C 0.013 Combustion (Leco)

s 0.020 Leco
Mn 0.051 Direct reading spect.
P 0.007 Direct reading spect.
A1 0.004 Spectrograph
Si 0.000^ Spectrograph
Sn 0.007 Spectrograph
Cr 0.008 Spectrograph
Co 0.006 Spectrograph
Pb 0.001 Spectrograph
Ni 0.0^6 Spectrograph
Mo 0.005 Spectrograph
Cu 0.10 Direct reading spect.
Va
Sb
As Less than 0.010 Direct reading spect.
Cb
Cd“ Less than 0.010 Direct reading spect.

Metallographic examination disclosed equiaxed grains

of ASTM size number 4 to 5 . The general appearance of the

grain structure is typical of ingot iron in the angular or

somewhat rugged grains.

Light cold working was done on the iron rod.

71

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 APPENDIX II

Colorimetric Determination of Ferric Chloride Concentration

A Bausch and Lamb Spectronic 20 colorimeter has been

used for the analysis of iron in the corroding solution. The

following procedure was used:

Iron wire of purity 99.8 6% was used for this calibration.

A small piece of wire weighing 0.100 grams was dissolved in

10 ml of 1:1 hydrochloric acid by heating the acid gently.

One millilitre of 30 percent hydrogen peroxide was added and

the solution was boiled till there was no evidence of further

evolution of chlorine gas.! After cooling, the solution was

diluted with acid of the desired normality to 100 ml. Thus

an iron solution of 1.79 x 10”^ molar concentration was

obtained. A solution of 1.79 x 10~3 molar concentration was

prepared by diluting 10 ml. of 1,79 x 10” ^ molar solution to

100 ml. with the acid of the desired normality. Finally by

various proportions of these solutions and pure acid, eight

solutions of different concentrations of iron were prepared.

A
The colorimeter was set at a wavelenth of 370 m M because

at this wavelength maximum absorbance was obtained as reported

by many investigators (^--1,^5 *^7) and also found by this author.

Wi t h the colorimeter set at this wavelength, transmittances

72

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 of standard solutions were read with a blank solution of

hydrochloric acid being taken as 100 percent transmission

and a graph of percent transmittance versus concentration

was plotted as shown in figure II-1 . This plot can be used

for both ferric and ferrous ion determination in the following

manner: An initial reading of the unknown sample yields

(Fe+++). Subsequent oxidation with a drop of 30% hydrogen

peroxide and rereading yields the total ion concentration.

,i i,

The latter figure minus the former gives (Fe ).

The effect of temperature on the intensity of ferric

chloride was also studied. A plot of transmittance versus

temperature as depicted in figure II-2 , shows that trans­

mittance decreases as the temperature is increased.

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 ?4

100

90

80

70
TRANSMITTANCE

6o

50
PERCENT

30

20

10

0 1 2 6
(Iron Concentration) x 10**, Moles/litre

FIGURE II-1 CALIBRATION CURVE FOR IRON ANALYSIS

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 75

90 -

80 _

70 —

6o
TRANSMITTANCE

50 —

40
PERCENT

30

20

10 —

20 30 40

TEMPERATURE, C°

FIGURE II-2 EFFECT OF TEMPERATURE ON TRANSMITTANCE

OF IRON SOLUTIONS

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX III

Detailed Calculations of Constants K-j_ and K2 in Equation (5.8)

A Under Anaerobic Conditions:

Equation (5.8) reduces to

SlEaL . Ki (HC1) exp ,.2^2,

v, a(Fe) -v exr> (+ SlLOO)

1 at (a ) 3 A ( h c i ) p B'-C

Substitution of the values for d(Fe) , V, A and

dt
(HC1), shows the average value of to be 13.1

B. Under Aerated Conditions;

Equation (5.8) becomes

diFel = .(A)3A (HC1) exp ^00) + k2 (Fo2 )°*5 (Fe)°'5 ]

dt - ___ ________ ________ d(Fe) _______ ________________

iALpTtHCir~exp (- 13. 1 + K2 (F0 2 )0 *5 (Fe)°‘5j

This equation can be written in the form

dt = dX^
C + Bxi

where C and B are constants

X is (Fe)

Now putting X'a = Y

76

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 77

then §X”£ £X a dY

dX = 2dYX^

* 2YdY

a +- ~ 2YdY
C + BY

Intergration of both sides gives

f a = / f MY
C + BY

dYBY
-if C + BY

- 2 f dy(C + BY - C
BJ C + BY

= i [ / dI- / § - 5 ^ ? dY J

t = “ ln(C + BY)
B b2

t = 2 (Fe)0 *^
3/k f) ir
K2\ - (HC1) exp (- -2|jp (P0 2 )

r
^2 x 13.1
(a'} (HC1) exp (- RT

[kZ (HCl) exp (- 3 ! m (P0 2 ) ° - 5 ] z

( 1/4 3/4
] In [ 13.1 (HCl) exp (- SMQ.) + K2 lA l (HCl)
/ L V RT ^ V

exp(- S | 0 0 ) { P O 2 )0,5 (pe )°-5 ] j

L
The average value of KR was found to be 1,18 x 10 .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX IV

4.02,7 N HCl Dissolution Runs

4500 rpm
2.84 sq. cm.
500 ml. volume

All Concentrations are in (Moles/litre) x 10^

Run 1 - 45°c, Air Run 2 - 4o°c, Air

Time (Fe ) (Fe) (Fe+'h) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0:5 0.2 0.8 0.6 0.5- 0.17 0.96 0.79

1.0 0.45 1.56 1.11 1.75 0.38 2.03 1.65
1.5 0.60 2.15 1.55 2.0 0.49 2.35 1.‘86
2.0 0.77 2.’90 2.13 2.5 0.6 2.8 2.2
2.5 1.06 3 -95 2.89 3.0 0.75 3.55 2.8
3.25 1.'39 5.5 4.11 3.5 0 .'86 4.J2 3.34
3.5 1.6 6.0 4.4 4.0 1.0 4.6 3.6
4.0 2.2 7.08 5.48 4.75 1.4 6.26 4.86
4.5 2.28 8.6 6.32 5.0 1.6 6.52 4.92
5.0 2.48 10.2 7.72 5.5 1.84 7.48 5.6 4
5.5 2.84 11.9 9.06

Run 3 - 35°C. Air Run 4 - 30°c, Air

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

1.0 0.2 1.19 0.99 0.5 0.16 0.81 0.65

1.5 0.27 1,65 1.38 1.0 0.23 1.0 0.77
2..0 0.3 6 2.15 1.79 1.5 0.30 1.52 1.22
2.5 0.49 2.72 2.23 2.0 0.40 1.82 1.42
3.0 0.55 3.16 2.61 2.5 0.45 2.06 1.61
3.5 0.67 3.75 3.08 3.0 0.5 2.41 1.91
4.25 0.82 4.8 3.98 3.5 0.65 2.73 2.08
5.0 1.12 5.96 4.84 4.5 0.79 3.5 2.71
5.5 1.24 6.6 5.36 5.0 0.85 4.25 3.05
5.5 0.96 4.85 3.89

78

Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission.
 79

All Concentrations are in (Moles/litre) x 10

Run 5 - 26°C, Air Run 6 - 45°c, n2

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour) V

0.5 0.1 0.5 0.4 0.5 0.0 0.77 0.77

1.0 0.14 0.83 0.69 1.0 0.0 1.38 1.38
1.5 0.19 1.01 0.82 1.5 0.09 1.69 1.6
2.0 0.22 1.26 1.04 2.0 0.12 2.3 2.18
2.5 0.2? 1.45 1.18 2.5 0.14 2.69 2.55
3.0 0.28 1.7 1.42 3.0. 0.14 3.35 3.21
3.5 0.35 1.93 1.58 3.75 0.14 3.95 3.81
4.0 0.40 2.2 1.8 4.5 0.18 5.0 4.82
4.5 0.45 2.39 1.94 5.0 0.20 5.5 5.3
5.0 0.45 2.57 2.12 5.5 0.20 6.0 5.8
5.5 0.46 2.8 2.34 6.0 0.36 6.68 6.32
o

n2 Run 8 - 35°C. n 2
o

Run 7 -
o

+++
Time (Fe+++) (Fe) (Fe++) Time (Fe ) (Fe) (Fe ')
(hour) (hour)

0.5 0.02 0.75 0.73 0.5 0.04 0.75 0.71

1,0 0.02 1.06 1.04 1.0 0.04 0.93 0.89
1.5 0.04 1.35 1.31 1.5 0.05 1.25 1.20
2.0 0.04 1.64 1.6 2.0 0.05 1.45 1.40
2.5 0.05 2.0 1.95 2.5 0.06 1.67 1.61
3.0 0.05 2.25 2.20 3.25 0.06 2. 10 2.04
3.5 0.05 2.5 2.45 3.5 0.07 2.12 2.05
4.0 0.10 2,8 2.7 4.0 0.09 2.45 2.36
4.5 0. 12 3.06 2.94 5.0 0.37 2.95 2.58
5.0 0.14 3.39 3.25 5.25 0.54 3.12 2.58
5.5 0.15 3.55 3.40

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 80

_4
All Concentrations are in(Moles/litre) x 10 •

Run 9 - 30°c, N 2 Run 10 - 26°C, n2

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 0.01 0.4 0.39 0.5 0.0 0.3 0.3

1.0 0.04 0.6 0.56 1.0 0.0 0.5 0.5^
1.5 0.04 0.81 0.77 1.5 0.01 0.67 0.66
2.25 0.04 1.02 0.98 2.0 0.01 0.86 0.85
2.5 0.04 1.11 1.07 2.5' 0.01 0.97 0.96
3.0 0.04 1.29 1.25 3.0 0.01 1.11 1.1
3.5 0.04- 1.4-5 1.41 3.5 0.01 1.26 1.25
4.0 0.04- 1.55 1.51 4-.0 O.Oif 1.46 1.42
^.5 0.04- 1.72 1.68 5.0 0.04- 1.67 1.63
5.0 0.04- 1.9 1.86 5.5 0.04- 1.77 1.73
5.5 0.04- 2,06 2.02 6.0 0.04- 2.0 1.96
6.0 0.06 2.2 2.14

Run 11 - 4-50C, °2 Run 12 ~ it-0°C, °2

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 1.1 2.5? 1.4-7 0.5 0.66 1.74- 1.08

0.75 1.52 3.81 2.29 1.0 1.52 3.75 2.23
1.0 2.0 5.25 3.25 1.5 2.55 6.4 3.85
1.5 3.52 9.0 5.4-8 2.0 3.4-0 9.2 5.8
2.0 4-.52 11.76 7.24 2.5 4.24 11.6 7.3 6
2.5 6.0 15.8 9.8 3.0 5.6 15.0 9.4-
3.0 7.2 22.0 14-.8 3.5 6.4 18.4- 12.0
3-5 8.76 25.5 16.74- 4-.0 7.42 24-.08 16.66
4.0 10.22 28.7 18.4-8 4-.5 8.75 2 7.65 18.9
4-.5 11.9 33.95 22.05 5.0 9.8 33.95 24.15
5.0 13.86 44.44 30.58
5.5 16.06 53.35 37.29

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 All Concentrations are in (Moles/litre) x 10*"^

Run 13 - 35°C, o2 Run 14 - 30°C, °2

+++
Time (Fe+++) (Fe) (Fe++) Time (Fe ) (Fe) (Fe++)
(hour) (hour)

0.25 0.28 0.93 0.65 0.5 0.57 1.46 0.89

0.5 0.52 1.59 1.07 1.0 1.0 2.45 1.45
0.75 0.78 2.18 1.40 1.5 • 1.45 3.6 2.15
1.0 1.17 3.06 1.89 2.0 1.87 4.86 2.99
1.25 1.46 3.75 2.29 2.5 2.68 6.1 3.^2
1.5 1.71 ^.5 2.79 3.0 2.92 7.8 4.88
2.0 2.3 6.4 4.1 3.5 3.^ 9.0 5.6
2.5 3.12 8.8 5.68 4.0 3.8 10.88 7.08
3.0 3 .68 11.0 7.32 *K5 4.24 12.64 8.40
3.5 4.08 13.76 9.68 5.0 4.6 14.44 9.84
4.0 4.64 15.8 11.16
4;5 5.2 20.4 15.2
5.0 5.8 24.0 18.2
5.5 6.3 28.00 21.70

Run 15 - 26°C, °2
Time (Fe+++) (Fe) (Fe++)
(hour)

0.5 0.4 1.0 0 .6

1.0 0.8 1.8 1.0
1.5 1.2 2.5 1.3
2.0 1.6 4.0 2.4
2.5 2.1 4.7 2.6
3.0 2.4 6.0 3.6
3.5 2.85 7.2 4.35
4,0 3.2 8.5 5.3
4.5 3.65 10.0 6.35
5.0 4.05 11.6 7.55
5.5 4.4 13.2 8.8

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX V

3.02 N HCl Dissolution Runs

4500 r.p.m.
2.84 sq. cm.
500 ml. volume

All Concentrations are in (Moles/litre) x 10

0
■3-
0
0
Run 16 - 45°C, Air Run 17 Air

1
Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)
(hour) (hour)

0.5 0.08 0.7 0.62 0.5 0.06 0.45 0.39

1.0 0.15 1.25 1.1 1.0 0.11 0.88 0.77
1.5 0.2.5 1.8 1.55 1.5 ' 0.20 1.35 1.15
2.0 0.34 2.3 1.96 2.0 0.30 1.73 1.43
2.75 0.43 3.1 2.67 2.5 O .36 2.14 1.78
3.0 0.52 3.35 2.83 3.0 0.41 2.58 2.17
3.5 0.61 3.9 3.29 3.5 0.48 3.1 2.62
4.0 0.66 4.6 3.94 4.0 0.55 3.6 3.05
4.5 0.8 5.5 4.7 4.5 0.63 4.25 3.62
5.0 0.87 6.05 5.18 5.0 0.70 4.8 4.1
5.5 0.76 5.35 4.59
6.0 0.83 6.05 5.22

Run 18 - 35°C, Air Run 19 - 30°c, Air

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++

(hour) (hour)

0.5 0.05 0.45 0.4 0.5 0.05 0.32 0.27

1.0 0.10 0.70 0.6 1.0 0.09 0.56 0.47
1.5 0.16 1.03 0.87 1.5 0.12 0.80 0.68
2.0 0.21 1.40 1.19 2.25 0.16 1.12 O .96
2.5 0 .2? 1.75 1.48 2.5 0.22 1.2 0.98
3.0 0.30 2.37 2.07 3.0 0.25 1.48 1.23
3.75 0.40 2,84 2.44 3.5 0.27 1.70 1.43
4.0 0.42 3.1 2.68 4.0 0.32 1.96 1.64
4,5 0,48 3.4 2.92 4.5 0.35 2.6 2.25
5.0 0.53 3.73 3.20 5.0 0.38 3-0 2.62
5.5 0.60 4.53 3.93 5.5 0.45 3.7 3.25
6.0 0.63 5.15 4.52 6.0 0.50 4.3 3.80

82

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 83

All Concentrations are in (Moles/litre) x 10

•£-
O
1

O
Run 20 - 26°C, Air Run 21

•0
02
Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)
(hour) (hour)

0.5 0.02 0.25 0.23 0.5 0.83 2.8 1.97

1.0 0.08 0.45 0.37 1.0 1.92 5.5 3.58
1.5 0.1 0.63 0.53 1.5 2.52 9.04 6.52
2.0 0.13 0.8 0.67 2.0 ■ 3.24 11.84 8.6
2.5 0.17 1.08 0.91 2.5 4.44 15.2 10.76
3.0 0.20 1.25 1.05 3.0 4.8 18.8 14.0
3.5 0.25 1.49 1.24 3.5 5.52 23.6 18.08
4.0 0.28 1.77 1.49 4.0 5.7 28.2 22.5
5.0 0.35 2.14 1.79 4.5 7.0 33.9 26.9
5.5 0.38 2.37 1.99 5.0 8.0 38.?0 30.7
6.0 0.41 2.7 2.29

Run 22 - 40°C, 02 Run 23 - 30°C, °2

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 0.71 2.3 1.59 0.5 0.7 0.97 0.27

1.0 1.73 4.7 2.97 1.0 1.15 2.1 0.95
1.5 2.3 6.75 4.45 1.5 1.65 3.3 1.65
2.0 3.0 9.9 6.9 2.0 2.1 4.8 2.7
2.5 3.65 13.0 9.35 2.5 2.62 6.3 3.68
3.0 4.28 16.72 12.44 3.0 2.92 7.68 4.76
3.5 5.02 19.8 14.78 3.5 3.6 9.36 5.76
4.0 5.7 24.0 18.3 4.0 3.88 11.68 7.8
4.5 6.3 28.0 21.7 4 5
. 4.4 13.4 9.0
5.0 6.9 32.0 25.1 5.0 4.64 15.4 10.76
5.5 '5A 18.0 12.6

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 84
-

All Concentrations are in (Moles/litre) x 10

Run 24- - 26°c, °2 Run 25 - 35°c, N2

*■*!
+
+
(Fe) (Fe++

CD
Time (Fe+++) (Fe) Time (Fe+++)
(hour) (hour)

0.5 0.2? 0.?6 0.49 1.0 0.0.3 0.82 0.79

1.0 0.73 1.88 1. 15 1.5 0.03 1.04 1.01
1.5 1.28 2.96 1.68 2.0 0.03 1.38 1.35
2.0 1.78 4.18 2.40 2.75 0.05 1.70 1.65
2.5 2.37 5.5 3.13 3.5 ■ 0.20 1.92 1.72
3.0 2.64 7.2 4.56 4.0 0.12 2.16 2.04
3.5 3.04 8.56 5.52 4.75 0.020 2.34 3.23
4-.0 3.52 10.2 6.68 6.0 0.050 2.72 2.6?
4.5 3.9 6 11.68 7.72 6.5 0.120 2.92 2.80
5.0 4.28 13.4 9.12 7.5 0.160 3.3 3.14
5.5 4.72 15.4 10.68

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX VI

5.37 N HCl Dissolution Runs

4500 r.p.m.
2.635 sq. cm.
500 ml. volume

All Concentrations are in (Moles/litre) x 10

f
Run 26 - 45° c , Air Run 27 - 45°C, Air

Time (Fe+++) (Fe) (Fe++) Time (Fe++-i-) (Fe) (Fe++)

(hour) (hour)

0.25 0.3 1.0 0.7 0.25 0.28 1.0 0.76

0.5 0.37 1.25 0.88 0.5 0.35 1.45 1.1
0.75 0.57 1.85 1.28 0.75 0.54 2.04 1.50
1.0 0.78 2.35 1.57 1.0 0.73 2.5 1.57
1.25 1.11 3.0 2.89 . 1.25 0.91 3.11 2.20
1.50 1.24 3.64 2.90 1.50 1.15 3.77 2.62
2.0 2.22 5.1 2.98 2.0 1.82 5.25 3.43
2.5 2.68 6.6 3.92 2.5 2.4 6.92 4.52
3.0 3.2 8.28 5.08 3.0 3.0 9.6 6.3
3.5 4.68 12.0 7.32 3.5 3.72 12.0 8.28
4.0 5.8 14.56 8.76 4.0 4.12 14.56 10.46
4.5 8.0 18.0 10.0 4.5 6.29 18.0 11.76
5.0 8.82 23.1 14.28 5.0 6.72 23.1 1.6.38
O
1

N2 2.95 sq.cm.
O

Run 28 - 35°c, Air Run 29

0

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.25 0.05 0.75 0.7 0.5 0.1 1.05 0.95

0.50 0.26 1.11 0.85 1.25 0.16 2.4 2.24
0.75 0.38 1.40 1.02 3.0 0.4 6.8 6.4
1.0 0.42 1.88 1.46 3.5 0.48 8.6 8.12
1.25 0.51 2.22 1.71 4.0 0.72 9.72 9.0
1.5 0.71 2.74 2.03 4.5 1.12 10.80 9.68
2.0 0.96 3.77 2.81 5.0 1.20 12.96 11.76
2.5 1.24 4.6 3.36 5.5 1.40 15.08 13.68
3.0 1.8 5.76 3.9 6 6 .0 1.6 15.72 14.12
4.5 2.68 9.84 7.16
5.0 3.32 11.80 8.48
5.5 4.52 14.28 9.76
6.0 4.96 16.60 11.64

85

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX VII

6,04 N HCl Dissolution Runs

4500 r.p.m.
2.84 sq. cm.
500 ml. volume
-4
All Concentrations are in (Moles/litre) x 10

0
Air

0
Run 30 - 45°C. Air

0
Run 31

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 0.47 1.71 1.24 0.5 O .36 1.48 1.12

1.0 1.2 3.0 1.8 1.0 • 0.72 2.53 1.81
1.5 2.13 4.25 2.12 1.5 1.47 3.95 2.48
2.0 3.88 6.84 2.96 2.0 2.1 5.56 3.46
2.5 4.2 8.8 4.6 2.5 3.2 7.24 4.04
3.0 5.6 12.0 6.4 3.0 4.36 9.12 4.76
3.5 7.8 15.48 7.68 3.5 5.5 11.8 6.3
4.0 10.84 18.6 7.76 4.0 7.24 14.2 6.96
4.5 12.0 22.2 10.2 4.5 7.62 16.2 8.58
5.0 14.5 26.0 11.5 5.0 9.8 19.4 9.6
0
0
0

Run 32 - 35°c. Air Run 33 Air

1

+
+
CD
Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe)
(hour) (hour)

0.5 0.17 1.01 0.84 0.5 0.11 0.82 0.?1

1.0 0.40 1.81 1.41 1.0 0.25 1.5 1.25
1.5 0.75 3.08 2.33 1.5 0.47 2.26 1.79
2.0 1.15 3.89 2.74 2.0 0.69 2.95 2.2 6
2.5 1.8 5.92 4.12 2.5 0.93 4.6 3.67
3.0 2.4 7.84 5.44 3.0 1.26 5.6 4.34
3.5 3.12 9.8 6.68 3.5 1.68 6,84 5.16
4.0 4.6 12.3 7.7 4.0 2.0 8.24 6.24
4.5 5.6 14.5 8.9 4.5 2.48 9.4 6.92
5.0 6.7 17.8 11.1 5.0 2.92 10.88 7.96

86

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 87

All Concentrations are in (Moles/litre) x 10“"4

Run 34 - 26°C, Air Run 35 - 40°C, n2

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

o.5 0.16 0.9 0.74 0.5 0.008 1.51 1.502

1.0 0.35 1.45 1.10 1.0 0.1 2.76 2.75
1.5 0.5 2.1 1.60 1.5 0.2 4.05 3.85
2.0 0.7 2.72 2.02 2.25 0 .4 7.6 7.2
2.5 0.9 6 3.55 2.59 2.50 0.44 8.48 8.04
3.0 1.35 4.15 2.80 3.0 0.68 10.84 10.16
3.5 1.80 5.40 3.60 3.5 0.92 14.4 13.48
4.0 2.08 6.64 4.56 4.0 1.28 16.6 15.32
4.25 2.44 6.80 4.36 4.5 1.50 21.3 19.8
4.50 2.52 7A 4.88 5.0 1.68 24.3 22.62
5.0 2.92 8.24 5.32

Run 36 - 35°cf N2 Run 37 - 30°C, n2 '

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 0.05 1.47 1.42 0.5 0.01 1.30 1.29

1.25 0.17 2.95 2.78 1.0 0.02 2.3 2.28
1.50 0.2 3.6 3.4 1.5 0.07 3.55 3.48
2.0 0.2.4 5.44 5.2 2.0 0.17 4.25 4.08
2.5 0.24 7.2 6.96 2.5 0.20 6.24 6.04
3.5 0.64 11.8 11.16 3.0 0.24 7.84 7.6
4.0 0 .64 14.8 14.16 3.5 0.25 8.8 8.55
4.5 0/92 17.0 16.08 4.0 0.28 10.48 10.2
5.0 1.2 22.8 21.6 4.5 0.44 12.32 11.88
5.0 0.68 13.80 12.12

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX VIII

2.416 N HCl Dissolution Runs

7500 r.p.m.
5.4 sq. cm.
500 ml. volume

All Concentrations are in (Moles/litre) x 10”^

Run 38 - 35°c. Air Rim 39 - 46°. Air

+++.
Time (Fe ) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)
(hour) (hour)

1.0 0.53 2.80 2.33 2.0 1.18 6.2 5.02

2.0 0.825 4.0 3.175 3.0 , 1.25 9.15 7.90
4.5 I.26 9.8 8.54 4.0 1.375 13.6 12.225
5.0 2.1 10.92 8.82 5.0 2.59 24.78 22.19
6.0 2.98 13.20 10.22 6.5 2.64 31.44 28.80
6.5 - 3.65 16.0 12.35 7.0 2.80 33.0 30.2

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX IX

Effect of Area on Dissolution Rate

4500 r.p.m.
4.027 N HC1
500 ml. volume
35°C
All Concentrations are in (Moles/litre) x 10“^

Run 40 - Air, 5 .28 sq. cm. Run 41 - 4.27 cm^, Air

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 0.32 1.52 1.20 0.5 . 0.16 0.55 0.39

1.0 0.58 2.4 1.82 1.0 0.26 0.90 0.64
3.0 1.4-5 6.56 5.11 1.5 0.36 1.342 0.982
4.0 1.90 9.0 7.1 2.0 0.45 1.88 1.43
4.5 3.88 15.84 11.96 2.5 0.53 2.5 1.97
5.0 4-. 1 19.5 15.4 3.0 0.65 3.24 2.59
5.5 4.3 22.5 18.2 3.5 0.72 4.20 3.48
6.5 4-.5 27.0 23.5 4.0 0.82 4.84 4.02
4.5 1.0 6.0 5.0
5.0 1.2 7.0 5.8
5.5 1.4 8.22 6.82
-3‘
co•

Run 43 - 1.43 cm2, Air

CM

Run 4-2 cm^, Air

1

Time (Fe+++ ) (Fe) (Fe++) Time (Fe+++) , (Fe) (Fe++)

(hours) (hour)

1.0 0.2 1.19 0.99 0.5 0.05 0.28 0.23

1.5 0.27 1.65 1.38 1.0 0.1 0.45 0,35
2.0 O .36 2 .1.5 1.79 1.5 0.14 0.56 0.42
2.5 0.49 2.72 2.23 2.0 0.20 0.64 0 .44-
3.0 0.55 3.16 2.61 2.5 0.26 0.81 0.55
3.5 0.67 3.75 3.08 3.0 0.29 1.0 0.71
4.25 0.82 4.8 3.98 3.5 0.35 1.21 0.86
4.75 1.0 5.6 4.6 4.0 0.39 1.32 0.93
5.0 1.12 5.96 4.84 4.5 0.42 1.56 1.14
5.5 1.24 6 .6 5.36 5.0 0.45 1.82 1.37
5.5 0.50 2.1 1.6

89

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 90

All Concentrations are in (Moles/litre) x 10“^

Run 44 - 5.72 cm2 . Np Run 45 - 4.26 cm2 , Np

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) -
(hour)

0.5 0.17 1.19 1.02 0.5 0.01 0.73 0.72

1.0 0.19 1.55 1.36 1.0 0.05 1.2 1.15
1.75 0.19 2.06 1.87 1.5 0.02 1.73 1.71
2.25 0.19 2.41 2.22 2.5 0.04 2.5 2.46
2.75 0.19 2.75 2.56 3.0 0.04 2.97 2.93
3.25 0.19 3.06 2.87 3.5 0.04 3.16 3.12
4.25 0.16 3-9 3.74 4.0 0.04 3.5 3.46
4.75 0.19 4.25 4.06 *K5 0.04 3.75 3.71
5.0 0.12 4.4 4.28 5.25 0.04 3.96 3.92
5.5 0.12 4.62 ^.5 5.5 0.05 4.2 4.15
6.0 0.15 5.0 4.85 6.0 0.05 4.9 4.85

Run 46 - 2.9 xm2 , Np Run 47 - 1.43 cm^, Np

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) <fe++)

(hour) (hour)

1.0 0.2 0.96 0.76 0.5 0.0 0.31 0.31

1.5 0.2 1.17 0.97 1.0 0.01 0.45 0.44
2.5 0.2 1.55 1.35 2.5 0.04 0.85 0.81
3.0 0.2 1.83 1.63 3.0 0.04 1.0 0.96
4.0 0.2 2.18 1.98 3.5 0.04 1.13 1.09
4.5 0.2 2.35 2. 15 4.0 0.04 1.25 1.21
5.0 0.2 2.58 2.38 4.5 0.04 1.40 1.36
5.5 0.2 2.73 2.53 5.25 0.04 1.63 1.59
6.0 0.24 3.16 2.92 5.5 0.04 1.71 1.67
6.0 0.05 1.82 1.77

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 91

4500 r.p.m.
6.04 N HC1
500 m l . volume
35°C

All Concentrations are in-(Moles/litre) x 10”^

O
Run 48 - 5-8 cm^f Air Run 49 - 4.11 cm^, Air

Time (Pe+++) (Pe) (Fe++) .Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.25 0.26 1.4 1.14 0.25 0.43 1.23 0.8

0.5 l'.O 2.95 1.95 0.5 0.5 1.8 1.3
0.75 0.92 4.5 3.58 0.75. 0.51 2.52 2.01
1.0 2.0 8.52 6.52 1.0 0.73 3.38 2.65
1.5 3.08 13.0 9.92 1.5 2.6 7.4 4.8
2 .0 4.62 18.48 13.86 2.25 2.68 9.8 7.22
2.5 7.02 2.43 17.28 2.50 3.28 10.8 7.56
3.0 10.26 29.1 18.84 3.0 4.6 14.8 10.2
3.5 13.36 38.8 25.44 4.25 8.46 23.22 14.76
4.0 13.53 46.75 33 22 4.5 9.12 24.9 15.78
^.5 15.68 59.5 43.82 5.0 10.45 31.9 21.45
5.0 17.6 68.0 50.4 5.5 12.65 35.75 23.1
5.5 18.24 77.6 59.36
-

Run 50 - 5.74 cm^, N£ Run 51 - 4.26 cm^, N 2

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 0.02 2.62 2.6 0.5 0.12 2.12 2.0

1.0 0.06 4.38 4.32 1.0 0.2 3-7 3.5
1.5 0.08 6.4 6.32 1.5 0.3 4.85 4.55
2.25 0 .40 11.8 11.4 2.0 0.4 7.72 7.32
2.5 0 .44 12.32 11.92 2.5 0.6 9.8 9.2
3.0 0.52 14.8 14.22 3.0 0.64 12.32 11.68
3.5 0.60 17.0 16.4 3.5 0.68 14.2 13.52
4.0 0.66 21.30 20.64 4.25 0.72 17.0 16.28
4.5 0.72 25.2 24.48 4.5 0.80 18.0 17.2
5.0 0.72 30.0 29.28 5.0 1.02 23.4 22.38

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 92

All Concentrations are in (Moles/litre) x 10**^

Run 52 - 1.42 cm^, Ng

Time (Fe+++) (Fe) (Fe++)

(hour)

0.5 0.008 0.8 0.792

1.0 0.01 1.37 1.36
1.5 0.04 2.0 1.96
2.0 • 0.0? 2.62 2.55
2.5 0.10 3.23 3.13
3.0 0.12 3.95 3.83
3.5 0.4 4.25 3-85
4.0 0.48 5.88 5.4
4.5 0.52 6.6 6.08
5.0 0 .6 7.72 7.12
................. - •

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX X

Effect of Volume on Dissolution Rate

4500 r.p.m.
2.84 sq. cm.
6.04 N HC1
40°C
Air

All Concentrations are in (Moles/litre) x 10**^

Run 53 - 400 ml . vol. Run 54 - 500 m l . vol.

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.5 0.36 1.66 1.30 0.5 ’ 0.36 1.48 1.12

1.0 0.8 3.15 2.35 1.0 0.72 2.53 1.81
1.5 1.36 4.25 2.89 1.5 1.47 3.95 2.48
2.0 2.28 7.04 4.76 2.0 2.1 5.56 3.46
2.5 3.2 9.2 6.0 2.5 3.2 7.24 4.04
3-0 4.32 11.6 7.28 3.0 4.36 9.12 4.76
3.5 6.04 15.08 9.04 3.5 5.5 11.8 6.3
4.0 7.84 18.0 10.16 4.0 7.24 14.2 6.96
4.5 9.18 23.7 14.52 *K5 7.62 16.2 8.58
5.0 12.12 27.96 15.84 5.0 9.8 19.4 9.6

Run 55 - 600 ml . vol.

Time (Fe+++) (Fe) (Fe++)

(hour)

0.5 0.35 1.3 0.95

1.0 0.72 2.31 1.59
1.5 1.14 3.3 2.16
2.0 2.28 5.24 2.96
2.5 3.12 6.9 3.78
3.0 4.0 8.72 4.72
3-5 4.4 10.08 5.68
4.0 6.16 12.6 6.44
4.5 7.16 14.8 7.5^
5.0 8.4 17.0 8.6

93

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 APPENDIX XI

Effect of Rotational Speed on Dissolution Rate

4.02? N HC1
2.84- sq. cm.
$00 ml. volume
35°C
Air

All Concentrations are in (Moles/litre) x 10“^

Run 56 - 0 r.p .m. Run 57 - 6000 r.p.m*

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) <Fe++)

(hour) (hour)

1.0 0.15 1.3 1.15 0.5 0 .14 0.7 0.56

1.5 0.17 1.7 1.53 1.0 0 .2$ 1.02 0.77
2.0 0.18 2.18 2.0 1.5 0.33 1.45 1.12
2.5 0.25 2.9 2.65 2.0 0.42 1.8? 1.4$
3.0 0.48 3.21 2.73 2.5 0.54 2.12 l.$8
3.5 0.65 4.1 3.45 3.0 0.6 2.5 1.9
4.25 0.93 5.0 4.07 3.5 0.68 3.06 2.38
4.75 1.24 5.92 4.68 4.2$ 0.81 3.75 2.94
5.0 1.4 6.08 4.68 4.$ 0.85 4.1 3.25
5.5 1.6 6.8 5.2 5.0 1.0 4.5 3.5
5.5 1.11 5.85 4.74
i-*
1

Run 58 r.p.m.
0
0
0

Time (Pe+++) (Fe) (Fe++)

(hour)

0.5 0.16 0.65 0.49

1.0 0.24 1.06 0.82
1.5 0.30 1.32 1.02
2.0 0.38 1.39 1.01
2.5 0.45 2.1 1.65
3.0 0.51 2.6 2.09
4.0 0 .66 3.45 2.79
4.5 0.75 3.80 3.05
5.0 0.8 4.25 3.45
5.5 0,89 4.75 3.86

94

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 95

6.04 N HC1
2.26 sq. cm.
500 ml. volume
35°c
Air

All Concentrations are in (Moles/litre) x 10“^

CM
0
0
Run 59 - 0 r.p .m. Run 60 r.p.m.

1
Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)
(hour) (hour)

0.5 0.7 3.0 2.7 0.25 0.28 0.4 0.12

1.0 1.36 5.8 4.44 0.75 0.63 1.3 0.67
1.5 3.28 8.9 5.72 2.0 1.6 3.55 2.95
2.0 4.48 12.2 7.72 2.5 2.3 5-3 3.0
2.5 6.84 16.2 IO.36 3.0 3.0 6.08 3.08
3.0 8.4 19.9 11.5 3.5 3.6 6.8 3.2
3-5 11.22 24.3 13.08 4.0 3.66 7.8 4.14
4,0 14.49 30.8 16.31 *K5 4.02 9.0 4.98
5.0 4.62 10.5 5.88
5.5 5.5 11.88 6.38

1
■«=■

CO
Mn

1
1

r.p.m. Run 62 r.p.m.

0
0
Run 6 l
0
0

Time (Fe+++) (Fe) (Fe++) Time (Fe+++) (Fe) (Fe++)

(hour) (hour)

0.25 0.2 0.8 0.6 0.5 0.42 1.6 1.18

0.50 0.245 1.02 0.775 1.5 1.26 3.1 1.84
0.75 0 .42 1.35 0.93 2.0 1.7 4.6 2.9
1.0 0.5 1.75 1.25 2.5 2.08 6.24 4.16
1.5 0.72 2.62 1.9 3.0 2.52 7.4 4.88
2.0 1.15 3.55 2.4 3.5 3.08 8.8 5.72
2.5 1.67 4.38 2.71 4.0 3.6 10.48 6.88
3.0 2.4 6 ,?6 4.36 4.5 4.4 12.0 7.6
4.25 5.44 12.4 6.96 5.0 5.04 14.0 8.96
4.5 6.04 14.48 8.44
5.0 7.2 17.0 9.8
5.5 7.6 19.4 11.8

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 96

All Concentrations are in (Moles/litre) x 10“^

Run 63 - 11000 r.p.m.

Time (Fe+++) (Fe) (Fe++)

(hour)

0,5 0.5 1.75 1.25

1.0 0.89 2.77 1.88
1.5 1.6 4.2 2 .6
2.0 2.0 5.44 3.44
2.5 2.4 6.84 4.44
3.0 3.0 8.82 5.82
3.5 3.72 10.8 7.08
4.0 4.32 12.?8 8.46

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 97

3.04 N HC1
2.90 sq. cm.
500 ml. volume
35°C
Nitrogen

All Concentrations are in (Moles/litre) x 10“^

Bun 64 - 3300 r .p.m. Run 65 - 6500 r.p.m.

+++,
.

Tirce (Fe ) (Fe) (Fe+ + ) Time (Fe+++) (Fe) <Fe++ )

(hour) (hour)

1.0 0.16 2.1 1.9^ 1.0 0.03 0.82 0.79

1.5 0.2 2.34 2.14 1.5 0.03 1.04 1.01
2.0 0 .22 2.54 2.32 2.0 ' 0.03 1.38 1.35
2.5 0.20 2.6 2.4 : 2.75 0.05 1.7 1.65
3.5 0.23 2.96 2.73 3.5 0.20 1.92 1.72
4.0 0.16 3.1 2.94 4.0 0.12 2.16 2.04
4.5 0.14 3.3 3.16 4.75 0.02 2.34 2.32
6.0 0.12 3.9 3.78 6.0 0.05 2.70 2.6?
6.5 0.11 4.04 3.93 6.5 0.12 2.92 2.80
7.5 0.11 4.6 4.5 7.5 0.16 3.3 3.14

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 VITA AUCTORIS

19^1 Bora in Dist. Mintgumary, W. Pakistan.

1963 Graduated from Panjab University, Chandigarh, India,

with the degree of B.Sc. in Chemical Engineering.

1965 Accepted into the Graduate School of University of

Windsor as candidate for the degree of M.A.Sc. in
Chemical Engineering.

98

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.