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Study on Recovery of Nitric Acid from Aqueous

Acidic Solution in Presence of Nitrate Ions


By

Sandeep Kumar Jaiswal


(ENGG1A201201040)
Bhabha Atomic Research Centre, Mumbai

A thesis submitted to the


Board of Studies in Engineering Sciences

In partial fulfilment of requirements


for the Degree of

MASTER OF TECHNOLOGY
of
HOMI BHABHA NATIONAL INSTITUTE

October, 2014
aa

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Homi Bhabha National Institute


Recommendations of the Thesis Examining Committee

As members of the Thesis Examining Committee, we recommend that the thesis prepared by
Shri SANDEEP KUMAR JAISWAL entitled Study on Recovery of Nitric Acid from
Aqueous Acidic Solution in Presence of Nitrate Ions be accepted as fulfilling the thesis
requirement for the Degree of Master of Technology.
Name
Member 1

Dr. A. K. Nayak

Member 2

Dr. S. Mukhopadhyay

Member 3

Dr. R. C. Bindal

Examiner

Dr. G. Sugilal

Guide / Convener

Dr. D. Mandal

Chairman

Dr. P. K. Tiwari

Signature

Final approval and acceptance of this thesis is contingent upon the candidates submission of
the final copies of the thesis to HBNI.

I hereby certify that I have read this thesis prepared under my direction and recommend that
it may be accepted as fulfilling the thesis requirement.

Date: 9th October 2014


Place: Mumbai

Dr D. Mandal
(Guide)

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Declaration
I, hereby declare that the investigation presented in the thesis has been carried out by me. The
work is original and has not been submitted earlier as a whole or in part for a degree / diploma at
this or any other Institution / University.

(SANDEEP KUMAR JAISWAL)

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DEDICATION

To
My loving parents

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Acknowledgements

It gives me immense pleasure and satisfaction to express my sincere and the deepest gratitude to
my guide Dr D. Mandal, Head, Materials Section, Chemical Engineering Division, Bhabha
Atomic Research Centre, Trombay, Mumbai-85 for his valuable guidance and advice throughout
this project work.

I am expressing my deep gratitude to Shri R. V. R. L Visweswara Rao who has inspired and
encouraged me to start my M.Tech project with his invaluable suggestions.

I also express my deep sense of gratitude to Shri C. V. R. Sharma; Chief Engineer; NFC Kota
Project, Shri P. A. Pratap; Project Director, NFC Kota Project, Shri P. B. Ojha; Technical Adviser
NFC Kota project, Shri T. K. Sinha, Scientific Officer-G and Shri Satyadeep, Scientific OfficerC, NFC Hyderabad for their supports during this project work.

I would like to acknowledge all the staff members of the Analytical Section of Control
Laboratory, NFC Hyderabad for providing all the analytical supports required for this project
work.

Date: 9th October 2014


Place: Mumbai

(SANDEEP KUMAR JAISWAL)

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Synopsis
Nitric acid is a commonly used dissolving agent in nuclear, chemical and metallurgical
industries and all these industries generate and discharge a huge quantity of effluent containing
free nitric acid and different metal nitrates. Disposal of effluents containing high nitrate
concentration is a serious and global problem. Nitrate contamination in drinking water causes
methemoglobinema, a disease in which oxygen-bearing capacity of blood is reduced, which is
called Blue-Baby-Syndrome. It is possible to recover and reuse nitric acid from effluents
containing free nitric acid. Experiments were carried out to recover nitric acid from aqueous
solution containing nitric acid in absence and presence of different metal ions viz., Na+, Mg+2,
Ca+2 and Al+3 by solvent extraction. In the present work, Tri-butyl phosphate (TBP) was
selected among several extractant because of its better selectivity towards nitric acid (HNO3),
overall superiority in operation, favourable physical properties and economics.

Experiments were conducted to study the recovery of HNO3 from aqueous solution in absence
and presence of different metal nitrates viz., NaNO3 , Ca(NO3 )2 , Mg(NO3 )2 and Al(NO3 )3

and of different nitrate concentrations (10-30 g/l) by using TBP (diluted with kerosene) as
solvent. All the experiments were carried out at room temperature. Mixing time for all the
extraction experiments were one minute and for the stripping experiments it was two minutes.
It was found that nitric acid can be extracted from effluent containing free nitric acid by using
dilute TBP (in kerosene) solution of organic to aqueous phase (O/A) ratio of 1:1. The
presence of various metal nitrates viz., NaNO3 , Ca(NO3 )2, Mg(NO3 )2 and Al(NO3 )3 of
different concentrations enhance the degree of extraction of nitric acid from aqueous nitric acid

solution. It was also found that the percentage of extraction of nitric acid in presence of
Al(NO3 )3 was higher than that of other metal nitrates. The extracted nitric acid was stripped

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out by using demineralized water with O/A ratio of 1:1. It was found that 69 to 76% of nitric
acid can be recovered in a single stage extraction process. The percentage extraction of nitric
acid can be increased by using higher concentration of TBP, as the concentration of TBP
increases; the percentage extraction of nitric acid increases. By recovering nitric acid form
effluent containing free nitric acid the total nitrate concentration in the effluent can be reduced,
which in turn can solve the disposal of nitrate bearing effluents. Moreover, the recovered nitric
acid can be reused, which in turn reduce the processing cost.

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Contents
Synopsis .................................................................................................................................................. vi
List of Figures ......................................................................................................................................... xi
List of Tables ........................................................................................................................................ xvi
Nomenclature ...................................................................................................................................... xxiv
Chapter 1 .................................................................................................................................................1
Introduction...............................................................................................................................................1
1.1

Background ................................................................................................................................1

1.2

Objectives ...................................................................................................................................5

1.3

Outline of the Thesis ..................................................................................................................6

Chapter 2 .................................................................................................................................................7
Literature Review ......................................................................................................................................7
2.1

Factors Affecting Extraction Process .......................................................................................11

2.0.1 Effect of Mixing Time ............................................................................................................11


2.0.2

Effect of Nitric Acid Concentration ..................................................................................12

2.0.3

Effect of TBP Concentration on HNO3 Extraction ...........................................................13

2.2

Equilibrium Constant for the System TBP-Water-Nitric Acid ................................................18

2.3

Solubility of TBP in Water and HNO3 Solution ......................................................................19

2.4

Studies on Third Phase Behaviour for TBP-Nitric Acid System .............................................22

2.5

Thermodynamics of Extraction of Nitric Acid by Using TBP Solution ..................................25

2.6

Effect of Inextractable Nitrate on Solubility of TBP in Water ................................................29

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Chapter 3 ...............................................................................................................................................32
Experimental Study .................................................................................................................................32
3.1

Brief Process Description .........................................................................................................32

3.2

Methodology ............................................................................................................................32

3.3

Experimental Setup ..................................................................................................................33

3.4

Chemicals & Reagents .............................................................................................................34

3.5

Experiments..............................................................................................................................35

3.6

Experimental Procedure ...........................................................................................................35

Chapter 4 ...............................................................................................................................................39
Results and Discussions ..........................................................................................................................39
4.1

First Set of Experiments in Absence of Metal Nitrates ............................................................39

4.2

Second Set of Experiments in Presence of 20 g/l Sodium Nitrate ...........................................44

4.3

Third Set of Experiments in Presence of 20 g/l Calcium Nitrate .............................................48

4.4

Forth Set of Experiments in Presence of 20 g/l Magnesium Nitrate ........................................52

4.5

Fifth Set of Experiments in Presence of 20 g/l Aluminium Nitrate .........................................56

4.6

Effect of Nitrate Concentration on the Extraction of Nitric Acid ............................................62

4.7

Nitric Acid Extraction in Presence of 10 g/l NaNO3 by TBP Diluted with Kerosene .............64

4.8

Nitric Acid Extraction in Presence of 10 g/l Ca(NO3)2 by TBP Diluted with Kerosene .........69

4.9

Nitric Acid Extraction in Presence of 10 g/l Mg(NO3)2 by TBP Diluted with Kerosene ........73

4.10

Nitric Acid Extraction in Presence of 10 g/l Al(NO3)3 by TBP Diluted with Kerosene..........77

4.11

Nitric Acid Extraction in Presence of 30 g/l NaNO3 by TBP Diluted with Kerosene .............80

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4.12 Nitric Acid Extraction in Presence of 30 g/l Ca(NO3)2 by TBP Diluted with Kerosene .........84
4.13

Nitric Acid Extraction in Presence of 30 g/l Mg(NO3)2 by TBP Diluted with Kerosene ........89

4.14

Nitric Acid Extraction in Presence of 30 g/l Al(NO3)3 by TBP Diluted with Kerosene..........93

4.15

Effect of TBP Concentration on the Extraction of Nitric Acid ..............................................100

4.16

Stripping of Nitric Acid from Extract ....................................................................................102

Chapter 5 .............................................................................................................................................104
Conclusions and future work ................................................................................................................104
5.1

Conclusions ............................................................................................................................104

5.2

Future Work ...........................................................................................................................106

References .............................................................................................................................................108

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List of Figures
Fig. 2.1 Effect of extractant type on the extraction efficiency of HNO3 and HAc (O: A =1,
single-contact 5 min, 22C, undiluted extractant, aqueous phase: 279 g/l HAc and 513 g/l
HNO3) [14]. ...............................................................................................................................9
Fig. 2.2 Variation of HNO3,org with time. TBP i = 0.363 M, 3, 1.13 M, O/A= 1, T = 25 C

[30]. .........................................................................................................................................12

Fig. 2.3 Variation of HNO3,org with 3, . TBP i = 0.363 M, O/A= 1,T= 25 C [30]. ......................13
Fig. 2.4 Variation of 3, with , 3, = 1.125 M. 3, =3.15 M, 3, = 6.35

M, O/A= 1 and T= 25 C [30]..................................................................................................14

Fig.2.5 Variation of log {HNO3,org / + . 3 } with logTBP .

3, =1.125 M.

3, =3.15 M, O/A= 1, T= 25 C [30]. ..............................................................................16

Fig.2.6 Effect of extractant concentration on the extraction efficiency of HNO3 and HAc

(O:A=1, single-stage contact 5 min, 22C, aqueous phase: 279 g/l HAc and 513 g/l
HNO3) [14]. .............................................................................................................................18
Fig.2.7 Variation of organic phase conductivity as the function of concentration of feed nitric
acid and TBP [42]....................................................................................................................24
Fig. 3.1 A snapshot of the experimental setup. .....................................................................................34
Fig.4.1 The extraction of nitric acid in the range of (14 M) by various concentration of tri-butyl
phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A = 1) and at
25C was determined in the absence of nitrate ions ................................................................41
Fig.4.2 Variation of nitric acid concentration in organic phase with TBP concentration (30 -80%)
in the absence of nitrates ion. ..................................................................................................42

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Fig.4.3 The variation of the nitric acid concentration in the extract with the initial concentration
of nitric acid in aqueous phase; which was varied from 14 M. 1.095 M (30 volume %)
TBP diluted with kerosene was used for the extraction with O/A= 1 and extractions were
carried out at 25C. ..................................................................................................................43
Fig.4.4 The extraction of nitric acid in the range of (14 M) by various concentration of tri-butyl
phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and at
25C was determined in presence of 20 g/l NaNO3. ................................................................46
Fig.4.5 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/l sodium nitrates. ..........................................................................................47
Fig.4.6 The extraction of nitric acid in the range of (14 M) by various concentration of tri-butyl
phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and at
25C was determined in presence of 20 g/l Ca(NO3)2. ............................................................50
Fig.4.7 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/l calcium nitrates. .........................................................................................51
Fig.4.8 The extraction of nitric acid in the range of (14 M) by various concentration of tri-butyl
phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and at
25C was determined in presence of 20 g/l Mg(NO3)2. ...........................................................55
Fig.4.9 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/lMagnesiumnitrates. .....................................................................................55
Fig.4.10 The extraction of nitric acid in the range of (14 M) by various concentration of tributyl phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and
at 25C was determined in presence of 20 g/l Al(NO3)3.........................................................58
Fig.4.11 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/l aluminium nitrates. ....................................................................................59

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Fig.4.12 Effect of extractant concentration on the extraction efficiency of HNO3 (O:A = 1, single
contact 3 min. 22C, aqueous phase; 4 M HNO3). ..................................................................61
Fig.4.13 Effect of TBP concentration on distribution coefficient of nitric acid in presence and
absence of nitrate ions(O: A = 1, single contact 3 min. 22C, aqueous phase: 4 M HNO3) ...62
Fig.4.14 Effect of nitrate ion concentration on the extraction of 2 M Nitric acid with 50% TBP
solution. ...................................................................................................................................64
Fig.4.15 The extraction of nitric acid in the range of (14 M) by various concentration of tributyl phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and
at 25C was determined in presence of 10 g/l NaNO3. ............................................................67
Fig.4.16 Variation of nitric acid concentration in organic phase with the initial concentration of
TBP in kerosene in presence of 10 g/l sodium nitrate in feed solution. ..................................68
Fig.4.17 Variation of the equilibrium concentration of nitric acid in extract with that in raffinate,
the experiments were carried out at 25oC with O/A ratio of 1:1 and feed solution
contains 10 g/l Ca(NO3)2 and with different concentration of TBP (30 - 80%) in
kerosene. ..................................................................................................................................72
Fig. 4.18 Variation of nitric acid concentration in organic phase with the initial concentration of
TBP in kerosene and in presence of 10 g/lCa(NO3)2 in feed solution. ...................................72
Fig.4.19 Variation of the equilibrium concentration of nitric acid in extract with that in raffinate,
the experiments were carried out at 25oC with O/A ratio of 1:1 and feed solution
contains 10 g/l Mg(NO3)2 and with different concentration of TBP (30 - 80%) in
kerosene. ..................................................................................................................................76
Fig.4.20 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 10 g/l Magnesium nitrates. ...................................................................................76

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Fig.4.21 The extraction of nitric acid in the range of (14M) by different concentration of tributyl phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A = 1), and
carried out at 25C was determined in presence of 10 g/l Al(NO3)3. ......................................79
Fig.4.22 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 10 g/lAl(NO3)3. ....................................................................................................80
Fig.4.23 The variation of nitric acid concentration in extract with that in raffinate for different
initial concentration of TBP (30 - 80%) in kerosene and in presence of 30 g/l NaNO3,
extraction experiments were carried outbyusingO/A ratio of 1:1 at 25oC nitric acid
concentration in feed solution were in the range of 14 M.....................................................83
Fig.4.24 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 30 g/l NaNO3. .......................................................................................................84
Fig.4.25 The extraction of nitric acid in the range of (14M) by various concentration of tri-butyl
phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and at
25C was determined in presence of 30 g/l Ca(NO3)2. ............................................................87
Fig.4.26 Variation of nitric acid concentration in organic phase with the initial concentration of
TBP in kerosene in presence of 30 g/l Ca(NO3)2 in feed solution. .........................................88
Fig.4.27 The extraction of nitric acid in the range of (14 M) by various concentration of tributyl phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and
at 25C was determined in presence of 30 g/l Mg(NO3)2 in feed solution. .............................92
Fig.4.28 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 30 g/l Mg(NO3)2. ..................................................................................................93
Fig.4.29 Variation of equilibrium concentration of nitric in extract with that in raffinate for
different initial concentration of TBP in kerosene and initial nitric acid concentration in
feed 4 M and in presence of 30 g/l Al(NO3)3. Organic to aqueous phase ratio, O/A= 1
and experiments were carried out at 25C. ..............................................................................96

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Fig.4.30 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 30 g/l Al(NO3)3. ...................................................................................................97
Fig.4.31 Effect of the presence of NaNO3 concentration on of the extraction nitric acid of initial
concentration 2 M by using TBP diluted with kerosene. ........................................................98
Fig.4.32 Effect of the presence of Mg(NO3)2 of different concentration in feed solution on of the
extraction nitric acid of initial concentration 2 M in feed solution by using TBP diluted
with kerosene ...........................................................................................................................98
Fig.4.33 Effect of the presence of Al(NO3)3 of different concentrations on the extraction nitric
acid of initial concentration 2M in feed solution by using TBP diluted with kerosene. .........99
Fig.4.34 Effect of the presence of Ca(NO3)2 of different concentrations on the extraction nitric
acid of initial concentration 2M in feed solution by using TBP diluted with kerosene. .........99
Fig.4.35 Effect of the concentration of TBP in kerosene on the extraction of nitric acid of initial
concentration of nitric acid in feed solution 1-4 M, in the absence of metal nitrate ions. ....102
Fig.4.36 Stripping of nitric acid from extract by using DM water with O/A ratioof 1:1 at constant
mixing time of 2 min. The average value of the % recovery of four set of experiments
for the initial nitric acid concentrations in aqueous solution of 1-4 M and extraction with
TBP solution was considered. ...............................................................................................103

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List of Tables
Table 2.1 Flash point of organic solvents, which are reported in literature for nitric acid
extraction.

Table 2.2 Effect of sodium nitrate on the solubility of TBP in aqueous phase.

31

Table 4.1 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and
organic phase, nitric acid was extracted by using 30% TBP (diluted with kerosene). 39
Table 4.2 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and
organic phase, nitric acid was extracted by using 40% TBP (diluted with kerosene). 39
Table 4.3 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and
organic phase, nitric acid was extracted by using 50% TBP (diluted with kerosene). 40
Table 4.4 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and
organic phase, nitric acid was extracted by using 60% TBP (diluted with kerosene). 40
Table 4.5 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and
organic phase, nitric acid was extractedby using 70% TBP (diluted with kerosene).

40

Table 4.6 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and
organic phase, nitric acid was extracted by using 80% TBP (diluted with kerosene). 41
Table 4.7 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

44

Table 4.8 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

44

Table 4.9 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

45

Table 4.10 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

45
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Table 4.11 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

45

Table 4.12 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

46

Table 4.13 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

48

Table 4.14 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

48

Table 4.15 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

49

Table 4.16 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

49

Table 4.17 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

49

Table 4.18 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

50

Table 4.19 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

52

Table 4.20 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

52

Table 4.21 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

53

Table 4.22 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

53

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Table 4.23 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted kerosene).

53

Table 4.24 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

54

Table 4.25 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

56

Table 4.26 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

56

Table 4.27 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

57

Table 4.28 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

57

Table 4.29 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

57

Table 4.30 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).
Table 4.31 Ionic radius of cation salting agents used in the experiments

58
60

Table 4.32 Detail of the Extraction data of 2M initial nitric acid solution with 50% TBP
solution in kerosene with 10-60 g/l concentration of NaNO3.

63

Table 4.33 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

65

Table 4.34 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

65

Table 4.35 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos
phase, nitric acid was extractedby using 50% TBP (diluted with kerosene).

65

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Table 4.36 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

66

Table 4.37 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

66

Table 4.38 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

66

Table 4.39 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

69

Table 4.40 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

69

Table 4.41 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

70

Table 4.42 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

70

Table 4.43 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

70

Table 4.44 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

71

Table 4.45 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

73

Table 4.46 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

73

Table 4.47 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

74

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Table 4.48 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

74

Table 4.49 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

74

Table 4.50 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

75

Table 4.51 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

77

Table 4.52 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

77

Table 4.53 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

78

Table 4.54 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

78

Table 4.55 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

78

Table 4.56 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

78

Table 4.57 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

81

Table 4.58 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

81

Table 4.59 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

81

Page | xx

Table 4.60 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

82

Table 4.61 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

82

Table 4.62 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

82

Table 4.63 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

85

Table 4.64 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

85

Table 4.65 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

85

Table 4.66 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

86

Table 4.67 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

86

Table 4.68 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

86

Table 4.69 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

89

Table 4.70 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

90

Table 4.71 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

90

Page | xxi

Table 4.72 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

90

Table 4.73 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

91

Table 4.74 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

91

Table 4.75 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

94

Table 4.76 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

94

Table 4.77 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

94

Table 4.78 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

95

Table 4.79 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 70% TBP (diluted with kerosene).

95

Table 4.80 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene)..

95

Table 4.81 Experimental data of log-log plots of HNO3,org /( + . 3 ) versus TBP in the
absence of metal nitrate.

101

Page | xxii

Publication
[1] Sandeep Jaiswal, R. V. R. L Visweswara Rao, D. Mandal, Recovery of Nitric Acid from
Aqueous Acidic Solution of Nitrate Ions, CHEMCON14, Chandigarh, 27-30 December 2014.

Page | xxiii

Nomenclature

Symbol

Notation

Unit

Concentration of hydrogen ion

[mol/l]

Initial concentration of nitric acid

[mol/l]

HNO3,org

Nitric acid concentration in organic phase

[mol/l]

HNO3,aq

Nitric acid concentration in aqueous phase

[mol/l]

Concentration of nitrate ion

[mol/l]

TBP i

Initial concentration of TBP

[mol/l]

TBP

Equilibrium concentration of TBP

[mol/l]

TBP.HNO3

Concentration of TBP and HNO3 complex

[mol/l]

K1

extraction of nitric acid using dilute TBP

3,

K eq
Kd

K dim
T

O/A

Thermodynamic equilibrium constant for

[l/mol]

Equilibrium constant

[l2/mol2]

Distribution coefficient

[-]

Equilibrium constant for dimerization of

[l/mol]

TBP in organic phase


Time

[s]

Organic (O) and aqueous (A) phase ratio

[-]

Page | xxiv

(volume/volume)

YH2 O

Mole fraction of water in organic phase

[-]

Mole fraction of TBP in organic phase

[-]

Mean activity coefficient of TBP

[-]

Mean activity coefficient of nitric acid in

[-]

YTBP

HNO3,aq

aqueous solution

Page | xxv

Chapter 1

Introduction

1.1 Background
Uranium dioxide (UO2 ) is produced by the reduction of uranium trioxide (UO3 ) and UO3 is

produced by the calcination of Ammonium Di-Uranate (ADU). The latter is produced by the
precipitation reaction of Uranyl Nitrate Pure Solution (UNPS) and ammonia or ammonium
hydroxide solution. The raw material either Magnesium Di-Uranate (MDU) or Uranium Ore
Concentrate (UOC) is dissolved in commercial grade nitric acid to obtain Crude Uranyl
Nitrate Slurry (CUNS). The CUNS is refined by solvent extraction process, using Tri-Butyl
Phosphate (TBP) as solvent to produce nuclear grade UNPS. The uranium in UNPS is
precipitated out as ADU by addition of ammonium hydroxide and or ammonia vapour in a
batch reactor at controlled rate.

CUNS is produced by dissolution of MDU or UOC in nitric acid and free nitric acid in
CUNS is maintained at 2.5-3 N. In the process of solvent extraction, uranium present in
CUNS is extracted counter currently by using 30-35 % TBP (diluted in kerosene) in slurry
extractor to obtain UNPS. The impurities along with undissolved solids go out along with
raffinate. The pure and loaded extract is then stripped counter currently with De-Mineralised
(DM) water in box type mixer-settler to obtain UNPS. During the purification by solvent
extraction process, all the chemical and nuclear impurities present in the raw material are
separated as Uranyl Nitrate Raffinate (UNR). The raffinate produced typically contains
uranium above specified environmental limit, due to which its direct disposal is not
Page | 1

permissible. The raffinate is sent to Active Effluent Treatment Facility (AETF) for further
treatment before disposal. In the AETF the effluent streams from the solvent extraction are
treated to meet the environmental guidelines before disposal through sale.

In AETF the UNR is treated in a second stage solvent extraction process using conditioned
solvent to bring down the concentration from to less than 5 mg/l of uranium for safe
disposal (as per Atomic Energy Regulatory Board, Govt. of India; guidelines, website:
http://www.aerb.gov.in/). This process requires conditioning of the lean solvent obtained
from stripping section and by using this treated solvent for extraction of residual Uranium
(U) from UNR. The Acidic Raffinate Slurry (ARS), produced in this process contains U
concentrations below disposal limit (5 mg/l) is sold off as a by-product. The free nitric acid
present in ARS may be recovered and reused to minimise the consumption of nitric acid as
well as to reduce the loading of nitrate ion concentration in the effluent.

Moreover, nitric acid is a commonly used dissolving agent in nuclear, chemical and
metallurgical industries [1, 2, 3]. It is also a commonly used acid for various organic
processes, fertilizer industries and lithium production from brine [4, 5, 6, 7]. As an end
result, a large quantity of aqueous acidic effluent containing nitrate ions is generated.
Disposal of such acidic effluent is a serious and global problem. Nitrate contamination in
drinking water causes methemoglobinemia [8], a disease in which nitrate ions react with
blood haemoglobin and convert it into methemoglobin [9]. Haemoglobin carries oxygen
from the lungs to other tissues but methemoglobin is incapable of carrying oxygen.
Formation of excess methemoglobin (more than 80% of total haemoglobin) causes death.
Nitrates are also known as carcinogen; as under some abnormal circumstances, it is reduced

Page | 2

to nitrite in stomach and form N-nitrosoamine, which is a postulated cause of stomach


cancer [10].

In recent years; various researchers attempted to separate metal ions or recover nitric acid
from acidic effluent containing free nitric acid [11-16]. Sato et al. [11] have developed an
adsorbent with a phosphonic acid di-butyl ester-type group by chloro-methylating styrene
and di-vinyl-benzene copolymer of different di-vinyl-benzene content following
phosphorylation for the preferential adsorption of nitric acid from effluent in presence of
HCl, NaCl, copper sulphate and nickel sulphate. They observed that nitric acid may be
adsorbed up to a concentration of 2 M. Kulkarni [12] had used Emulsion Liquid Membrane
(ELM) produced by using tri-n-octyl-phosphine oxide and sodium carbonate for the
preferential separation of uranium (VI) ions from aqueous nitric acid solution in presence of
Fe+3, Ca+2 , and Mg +2 ions. Stankovic et al. [13] used calix-4-arene amide derivatives to

separate silver ion from nitric acid solution. Shin et al. [14] developed a process to recover
nitric acid from the waste stream containing acetic acid, hydrofluoric acid, and silicon
generated from wafer industry using solvent extraction with Tri-Butyl Phosphate (TBP).
Zakharchenko et al. [15] developed sorption materials; by using multi-walled carbon

nanotubes; Taunit, a solid-phase extractant and a polymer composites which has high
sorption ability for the recovery of radionuclide from nitric acid solutions.

Lan et al. [16] used diffusion dialysis with homogenous anion exchange membrane for the
recycling of spent aqueous nitric acid solution containing Li+, Na+, K+, Mg+2 and Ca+2 ions.
Biswas et al. [17] evaluated the use of di-nonyl phenyl phosphoric acid (DNPPA) and its
synergistic mixtures with oxygen donors for extraction and recovery of uranium from
aqueous nitric acid solution.

Page | 3

Tri-Butyl Phosphate (TBP) is generally used for the purification of crude uranium, thorium
and plutonium from nitric acid medium by solvent extraction [18]. It is known that TBP can
extract nitric acid from aqueous solution.
Hesford

and

Mckay

[19]

reported

that

TBP

extracts

acids

in

the

order

HF HClO4 > HNO3 >H3 PO4 > HCl > H2 SO4 in a pure system. The extraction of nitric acid

may be enhanced by the addition of H3 PO4 and nitrate salts in the aqueous phase [20] and

the extraction of nitric acid is reduced by increasing the concentration of fluoride ions (e.g.,
HF, MgF2 etc.) in the feed solution [21].

Lee et al. [22] conducted experiments for the recovery of valuable metals and recovery of
nitric acid from the spent nitric acid solutions produced by dissolving Printed Circuit Board
(PCB). They found that 95% extraction of nitric acid was possible by using 50% TBP in
five counter-current stages at the volume ratio of organic (O) to aqueous (A) phase of 3:1,
from a feed solution containing 250 g/l nitric acid. Distilled water was used to strip nitric
acid.
Palatyand Bendova [23] studied the separation of nitric acid and ferric nitrate through an
anion-exchange membrane in a two-compartment mixed cell, and found that below 3%
partial flux of ferric nitrate, the membrane can be considered a very good separator for an
HNO3 and Fe(NO3 )3 mixture. Palaty and Bendova [24] also studied the separation of nitric

acid and sodium nitrate through an anion-exchange membrane in a two-compartment mixed


cell and found that nitric acid permeates well through this membrane, while sodium nitrate
is not efficiently rejected. Bell et al. [25] have studied the feasibility ofN, N, N , N - tetra-

octyl-di-glycol-amide (TODGA) for the extraction of nitric acid, by using activity based
calculations using thermodynamics based models.

Page | 4

In the solvent extraction of uranium from aqueous nitric acid solution by using TBP (diluted
with kerosene) a fraction of nitric acid is also extracted in the organic phase. The
concentration of nitric acid in raffinate normally varies between 2.5 to 3 N and in general it
contains nitrate ions of Na+ , Ca+2 , Mg +2 , Al+3 etc. of concentration about 50-60 g/l.
Significant works on the extraction of nitric acid from effluent are reported in literature.
Few attempts were made for the recovery of nitric acid from effluent by extracting with
dilute TBP solution. Limited information is available in literature regarding the effect of the
presence of various metal nitrates on the extraction of nitric acid by using TBP (diluted with
kerosene). Some works are reported on the solubility of TBP in water in presence of metal
nitrates but no information is reported about how the distribution coefficient of nitric acid
varies in the presence of various metal nitrates. It seems that in this field much work has not
been carried out and so much information is not available in literature.

In the present study; experiments were carried out for the recovery of nitric acid for reuse
from the effluent containing free nitric acid, so that total nitrate concentration of the effluent
can be reduced. The experimental details and results are discussed in this thesis.

1.2 Objectives
The objectives of the present study are as follows.

Investigation on the effect of different metal nitrates on the recovery of nitric acid
from aqueous solution containing free nitric acid.

Investigation on the effect of the concentrations of different metal nitrates on the


recovery of nitric acid from aqueous solution containing free nitric acid.
Page | 5

To minimise the loading of nitrate ion (NO3 ) concentration in effluents.

1.3 Outline of the Thesis


The thesis is divided into six Chapters. This chapter (i.e., Chapter 1) covered the
introduction of the thesis topic which includes background and objectives of the project
work. Chapter 2 includes literature review on the project topic. Details of the experimental
works have been presented in Chapter 3. Results and discussions are presented in Chapter
4. Finally, the conclusions and suggestions are discussed in Chapter 5.

Page | 6

Chapter 2

Literature Review

TBP is a phosphorus-containing compound with molecular formula (C4H9)3PO4, is prepared


by reaction of phosphorus oxy-chloride with butyl alcohol [1]. It is an organic liquid used as
a solvent for cellulose esters, lacquers and natural gums, in the manufacturing of plastics
and vinyl resins, as a metal extractant, as a base stock in the formulation of fire-resistant
hydraulic fluids for aircraft and as an antifoaming agent. During the past few years, the
utilization of TBP as an extractant in the dissolution process in conventional nuclear fuel
reprocessing has increased considerably; TBP is an excellent solvent for the extraction of
different inorganic salts [1]. The metal nitrates consist of one or all of uranyl nitrate,
plutonium nitrate, thorium nitrate, fission product nitrates or salting agents. Although other
solvents may extract these metal nitrates more efficiently, TBP is chosen for its overall
superiority in operation, safety, physical properties, radiation resistance, and economics.
One of the most desirable attributes of TBP is its high flash point (146C) compared with
other solvents except Tri-octyl phosphate having flash point 216C .Flash points of various
organic solvents are given in Table 2.1.

Tri-octyl phosphate has higher flash point compared to TBP but its extractability is poor for
nitric acid as discussed. Tri-n-Octyl-Phosphine Oxide (TOPO) is a good solvent which
extracts nitric acid better than TBP, but recoverability is poor. Therefore; TBP has been
chosen as a solvent for recovery of nitric acid from aqueous acidic solution.

Page | 7

Table 2.1 Flash point of organic solvents, which are reported in literature for nitric acid extraction.

Organic solvent

Flash point [C]

Decanol

108

Octanol

81.1

Heptanol

73

Hexanol

63-73

2-ethylhexyl alcohol

73

Tri-octyl phosphate

216

TBP

146

TOPO

110

Several neutral solvents were studied for their effectiveness to extract HNO3 preferentially.
An undiluted solvent was used as the organic phase in all cases. The results are presented in
Fig.2.1 and it was found that solvents such as 2-ethylhexyl alcohol (EHA), decanol, octanol,
heptanol and hexanol were more selective for CH3COOH (HAc) over HNO3. Tri-octyl
phosphate (TOP) and TBP showed more preferential extraction of HNO3 compared to HAc.
The extraction of HNO3 was about 46 % against a co-extraction of 32 % HAc in case of
TBP in a single contact. The corresponding values in case of TOP were 35 and 22 % for
HNO3 and HAc, respectively. The high polarity of the phosphoryl (P=O) group in TBP and
TOP enables it to act as a strong Lewis base and as a result it can form acidbase complex
when contacted with strong acids. Finally, TBP was chosen for the extraction of HNO3 for
its overall superiority in operation, favourable physical properties and economics.
Therefore, all further experiments were carried out using undiluted TBP, except extractant
concentration study where kerosene was used as a diluent [14].

Page | 8

HNO3
HAc

70

% Extraction (E, %)

60
50
40
30
20
10
0
EHA

Decanol

Octanol

Heptanol

Hexanol

TOP

TBP

Solvent

Fig. 2.1 Effect of extractant type on the extraction efficiency of HNO3 and HAc (O: A =1, singlecontact 5 min, 22C, undiluted extractant, aqueous phase: 279 g/l HAc and 513 g/l HNO3) [14].

The TBP is always diluted in an organic matrix, or diluent, to improve the physical
characteristics of the organic phase [1]. The diluent reduces the viscosity and density of the
organic phase and improves the phase separation characteristics and reduces criticality
concerns by limiting the maximum actinide concentration in the organic phase. The diluent
is chosen on the basis of radiation stability and inertness to the species in the solvent
extraction process. From a purely technical perspective, the alkane hydrocarbon dodecane,
C12H26 is the best diluent to use because it is inert and highly radiation resistant. Dodecane
can be purified to be free of aromatics that can react with some of the components in the
solvent extraction environment. However, dodecane is very expensive and for this reason,
purified kerosene or kerosene-like diluents such as; AMSCO-125-90 W, that have properties
nearly equivalent to those of dodecane are used instead.The tridentate ligand TODGA (N,
N, N , N tetra-octyl-di-glycol-amide) is the leading example of this class of ligands that can

also be used for the extraction of nitric acid [1].

Page | 9

In the extraction of uranium from acidic uranyl nitrate solution; not only TBP but also nitric
acid distributes itself between the organic and the aqueous phases. It was observed that the
solubility of TBP decreases with increase in the concentration of nitric acid in presence of
nitrate salt viz., sodium nitrate and calcium nitrate solutions in the aqueous phase [26].
Sodium nitrate and calcium nitrate are salting agent which reduces the solubility of TBP in
the aqueous phase. Sodium nitrate and calcium nitrate do not form solvates with TBP like
other metal nitrates and hence, they are inextractable metal nitrates. Hesford and Mckay
[27] had studied extraction of acidic uranyl nitrate solution with TBP (diluted with
kerosene). They observed that the extraction of extractable nitrates by TBP increases in
presence of inextractable metal nitrates because of lack of competition for complex
formation and salting-out effect of inextractable nitrates.

Alcock et al. [28] have investigated the salting out effect of TBP in presence of nitric acid
and sodium nitrate and found that TBP salted out more in sodium nitrate as compared to
nitric acid because nitric acid is an extractable but sodium nitrate is not extractable by TBP.
The pressure exerted by inextractable metal nitrates to salt out TBP depends on their ionic
radius and ionic strength. The small ionic radius and low ionic strength of sodium nitrate as
compared to calcium nitrate has resulted in lower solubility of TBP in the aqueous phase
and higher distribution ratio value of TBP.

Xianhong and Zhou [29] studied the extraction kinetics of nitric acid by TBP in heptane in
an improved Lewis cell. The activity of component was calculated by Pitzeris equation [29]
for aqueous phase and UNIFAC model for organic phase. From the calculated mass transfer
coefficient and mass transfer resistance, it was concluded that the main mass transfer
resistance in the extraction process came from the diffusion resistance in the boundary layer

Page | 10

of organic phase. The mean relative deviation between experimental results and calculation
values by using the model was found within 2.5%.

2.1 Factors Affecting Extraction Process


The extraction of nitric acid and hexavalent uranium from nitric acid and nitric acid
containing uranium (VI) media by Tri-Butyl Phosphate (TBP) diluted with kerosene was
studied by Schulz et al. [30] and all factors affecting the extraction process (time of mixing,
uranium concentration, nitric acid concentration, TBP concentration, temperature) were
investigated.

The previous investigators have studied parameters like time of mixing, uranium
concentration, nitric acid concentration, TBP concentration and temperature on the
extraction of nitric acid by TBP diluent system. However, the effects of presence of
inextractable metal nitrates were not studied earlier. In the present experimental work the
effect of the presence of inextractable metal nitrates on the extraction of nitric acid were
investigated.

2.0.1 Effect of Mixing Time


Schulz et al. [30] had used equal volume (25 ml) of 0.363 M TBP (in kerosene) and 1 M
nitric acid and mixed together at 25C for various time intervals to study the effect of time of
mixing to attend the equilibrium. Fig. 2.2 shows the variation of nitric acid concentration in
the organic phase against time. It was found that 0.5 minute was the minimum time to reach
equilibrium.

Page | 11

2.0.2 Effect of Nitric Acid Concentration


Schulz et al. [30] had studied the extraction of nitric acid from aqueous solution with initial
concentration of nitric acid in the range of 0.56.35 M by using 0.363 M (i.e.,10 volume %)
TBP diluted with kerosene of organic to aqueous phase (in volume) ratio (i.e., O/A= 1) and
at 25C. Their experimental results are shown in Fig. 2.3, which indicates that the
concentration of nitric acid in the organic phase increases with the increase in the
concentration of nitric acid in the aqueous phase.

HNO3 concentration in organic phase [mol/l]

0.06

0.05

0.04

0.03

0.02

0.01

0.00
0

Time [min.]

Fig. 2.2 Variation of , with time. = 0.363 M, , = 1.13 M, O/A= 1,


T = 25 C [30].

Page | 12

HNO3 concentration in organic phase [mol/l]

0.5

0.4

0.3

0.2

0.1

0.0
0

Initial HNO3 concentration in aqueous phase [mol/l]

Fig. 2.3 Variation of , with , . = 0.363 M, O/A= 1, T= 25 C [30].

2.0.3 Effect of TBP Concentration on HNO3 Extraction


Schulz et al. [30] had studied the effect of the TBP concentration in kerosene on the
extraction of nitric acid from aqueous solution of initial nitric acid concentration of 1.125,
3.15, 6.35 M with O/A ratio of 1:1 and at 25C. Fig. 2.4 shows the variation of nitric acid
concentration in the organic phase against initial TBP concentration. It was found that the
concentration of nitric acid in the organic phase increases linearly with increase in initial
TBP concentration (in kerosene).
Page | 13

Schulz et al. [30] proposed the mechanism for the extraction of nitric acid by TBP as shown
in Reaction (1).

H++ NO3+ TBP

TBP.HNO3

(1)

The equilibrium constant for the Reaction (1) can be written as shown in Eq. (2).

Keq =

. 3

(2)

+ . 3 .

HNO3 concentration in organic phase [ mol/l ]

0.8
1.125 M Nitric acid
3.15 M Nitric acid
6.35 M Nitric acid

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Concentration of TBP in organic phase [ mol/l ]

Fig. 2.4 Variation of , with , , = 1.125 M. , =3.15 M, , = 6.35 M,


O/A= 1 and T= 25 C [30].

Page | 14

Schulz et al. [30] considered the dimerization of TBP in the organic phase as follows and
the

equilibrium

constant

for

dimerization

of

TBP

in

organic

phase,

K dim is shown in Eq. (3) and its value determined by them is 2.6.
2TBP

(TBP)2

K dim =

()2

(3)

From the mass balance of TBP, following equations (4-6) may be written.

CTBP = CTBP - 2C(TBP)2 - CTBP.HNO3

(4)

1+

CTBP =
where, = 1 8KdimCHNO3

(5)

4Kdim

org

+ 8KdimTBP i

(6)

Taking the logarithm of both sides of Eq. (2) and rearranging, we obtain,

log

where,

.3

= logKeq + logTBP ,

.3 = 3

(7)

Page | 15

The log-log plots of 3

/ ( + . 3 ) with TBP gave two straight lines, with a slope

of 1.3 and 1.18 and regression coefficients of 0.999 and 0.997 for 1.13 M and 3.15 M nitric
acid concentration, as shown in Fig. 2.5, which suggests that one molecule of HNO3 was
extracted with one molecule of TBP [30]. The equilibrium constant for the extraction
reaction of nitric acid by TBP/kerosene was found to be 0.347 0.077 l2/mol2 for 1.13 and
3.15 M nitric acid concentration.

The partition of nitric acid between water and TBP/kerosene in absence of metal nitrates at
25C was studied. The extracted nitric acid in the organic phase is in the form of a 1:1
compound HNO3.TBP. The equilibrium constant of the extraction reaction was found to be
Keq = 0.347 l2/mol2.

Fig. 2.5 Variation of log

with log . , =1.125 M. , = 3.15 M, O/A= 1,


T= 25 C [30].

Page | 16

The effect of the TBP concentration on the extraction efficiency of HNO3 and CH3COOH
(HAc) with O/A ratio of 1:1 and at 22C has also been studied and the results are shown in
Fig. 2.6. It was observed that the extraction of nitric acid increased from19 to 46% (Kd =
0.230.85) in a single contact when TBP concentration increased from 20 to 100% [14].

During the same period, the co-extraction of HAc also increased from 9.4 to 32.2% ( Kd =
0.100.47). In the extracted species, the protons of an acid can form a hydrogen bond with
an oxygen atom of TBP molecules and thus the co-extraction of HAc together with HNO3 is
quite reasonable. Generally, the extraction of an acid tends to be enhanced by the commonion effect of protons that is produced by the dissociation of the acid, and reduced by the
competing extraction of another acid. To study the effect of HAc presence in feed solution,
another experiment was carried out. In that case, a synthetic solution was prepared
containing only nitric acid having the same concentration to that of actual solution. It was
observed that, the extraction efficiency of HNO3 increased by 1214% in case of a single
acid compared to a binary mixture of acids (HNO3 and HAc) by using TBP of same
concentration. This showed that; the extraction of HNO3 was suppressed by the coextraction of HAc as both may be chelating with the same functional group.

The log-log plots of 3

/ ( + . 3 ) with TBP gave straight lines with a slope of

1.88 and regression coefficients of 0.99, suggesting that two molecules of HNO3 was

extracted by one molecule of TBP. However, the mechanism is much more complicated
than mentioned above, with the involvement of water in the complex formation as suggested
by several investigators [20, 31]. Another parameter that has significant importance for
plant designing is the phase separation time. It was observed that, phase separation time
Page | 17

increased from 20 to 80 s, when TBP concentration increased from 20 to 100%. No thirdphase formation was observed in the experimental conditions used in the previous studies
[20, 31].

2.2 Equilibrium Constant for the System TBP-Water-Nitric Acid


Collopy and Cavendish [32] determined, the equilibrium constant for the reaction of TBP
with associated nitric acid was calculated as 19.9 0.5. The equilibrium distribution
constant for the partition of associated nitric acid in to TBP was determined as 0.19. The
equilibrium constant obtained were used to calculate the concentration of associated nitric
acid in dilute aqueous nitric acid solutions. These calculations were made from the
equilibrium distribution curve for nitric acid between TBP and water at 25oC over the
concentration range of 0-12 M aqueous nitric acid.

50

Percentage Extraction, E [%]

45
40
35
30
25

HNO3

20
15

HAc

10
5
20

40

60

80

100

TBP concentration in organic phase [volume %]

Fig. 2.6 Effect of extractant concentration on the extraction efficiency of HNO3 and HAc (O/A=1,
single-stage contact 5 min, 22C, aqueous phase: 279 g/l HAc and 513 g/l HNO3) [14].

Page | 18

As we know that a stable, equimolar complex was formed by the reaction of associated
nitric acid with TBP. It was concluded that this same reaction takes place between TBP and
associated nitric acid in two phase system TBP-H2O-HNO3. Collopy and Cavendish [32]
concluded that as the associated nitric acid present in aqueous nitric acid solution these two
phase system then can be represented by an equilibrium reaction in the organic phase as
shown in Reaction (8).

HNO3aq + TBPorg TBP. HNO3 org

(8)

The equilibrium curve for the distribution of nitric acid between TBP and water at 25oC
showed that the ratio of total nitric acid in the TBP phase to the total nitric acid in the
aqueous phase decreases with increasing aqueous nitric acid concentration until a constant
value is obtained.

2.3 Solubility of TBP in Water and HNO3 Solution


Burger and Forsman [33] have reported the values of the solubility of pure TBP and of TBP
in an inert diluent in water and in solutions of nitric acid of various concentrations. The
solubility of pure TBP in water was about 0.4 g/1 at 25C. When the TBP was diluted with
an inert substance insoluble in water, the solubility of TBP was found to decrease. The
presence of salts in the aqueous phase also decreased the solubility markedly. Similarly, the
solubility of TBP decreased slowly with increasing nitric acid concentration because of
competing effects such as the formation of TBP-HNO3 complexes. The solubility of water
in TBP-diluent mixtures varied from 64 g/l in pure TBP to about 0.06 g/1 in the pure
paraffin-type diluent. A comparison of several analytical methods used for determining the
solubility of TBP in aqueous solutions was also done.
Page | 19

Higgins et al. [34] have studied the effect of different electrolyte and temperature ranging
from 5 to 50C on the solubility of TBP in water. The salting coefficients at 25C for all the
electrolytes tested, excepting nitrates, have been correlated with the Gurney unitary partial
molal electrolyte entropy concept.

Tuck [35] had carried out experiments to measure viscosity of extract solutions of HNO3 in
TBP and TBP-water and TBP-anhydrous nitric acid mixtures and discussed the interactions
involved between like and unlike molecules. The viscosity varies with the mole fraction of
the species involved were interpreted in terms of strength of the interaction in the viscousflow transition state. Since the species involved have similar molar volumes, assumptions
were made from the viscosity to derive excess free energy of at different mole fractions.
Bullock and Tuck [36] had measured the mutual solubility of the two phase water-TBP
system. Nuclear magnetic resonance studies of solutions of water in TBP showed that the
structure of such solutions was more complex than suspected. The results obtained were
explained in terms of the formation of linear and chain polymers of varying complexity. The
model showed that the solubility of TBP is temperature dependent in both water and
aqueous nitric acid and also dependent of the concentration of nitrate ions in aqueous
solution.

Hardy et al. [37] studied distribution of nitric acid between aqueous phase and 100% TBP
and measured the densities of both the phases at equilibrium. They have determined the
solubility of lithium, sodium, potassium, caesium and ammonium thiocyanate and rubidium
thiocyanate in TBP. They found that the solubility decreased with increasing cation size,
except for ammonium salts. The values of ammonium salts were high due to the hydrogenbonding between NH4+ and the phosphoryl oxygen of the solvent.

Page | 20

Yamamoto [38] has determined the solubility of nitric acid in the organic phase by
measuring the dielectric property of the system. The dielectric properties of the organic
phase i.e. 30% TBP-n-dodecane-HNO3-H2O system and HNO3-H2O-UO2(NO3)2 system
were measured with a concentric capacitance cell, for in-line HNO3 monitoring in the
organic phase. It was found that the variation in the dielectric constant, caused by the
variation in the extracted HNO3, was markedly greater than that caused by the same molar
variations of H2O and UO2(NO3)2.

Swain et al. [39] had measured viscosities and densities of different binary liquid mixtures
of TBP with benzene, toluene and o-xylene at 30, 35 and 40C. The non-idealities reflected
in mixture viscosities have been expressed in terms of excess viscosities. A Redlich-Kistertype equation was fitted to the binary -X-T data for each system.

Tripathi and Ramanujam [40] had examined the radiation-induced changes in density and
viscosity of 30% TBP-dodecane-nitric acid system. It was observed that the increase in the
density becomes significant with increasing nitric acid concentration in the solvent,
HNO3.TBP concentration, and absorbed radiation dose, which concurrently leads to a much
sharper increase in the viscosity of the solvent. The extent of increase in the viscosity was
found to be significantly enhanced by gamma radiolysis and was a function of absorbed
dose. Gasliquid chromatography (GLC) and infrared (IR) analysis of the treated solvent
has revealed the radiation induced polymerization and nitration of the hydrocarbon diluent
which has resulted in increased viscosity. Tripathi and Ramanujam also found that a
considerable increase in the viscosity of the solvent with the presence of small amount of
radioactive species remaining in the solvent due to incomplete solvent purification.

Page | 21

Wright and Hartmann [41] have published a review paper by referring to more than 100
publications on physical and chemical properties of TBP-diluent-nitric acid systems. The
data on the kinetics of degradation products of TBP reported by different authors is also
cited. Wright and Hartmann reviewed the works of various investigators who investigated
the effect of physical properties of solution TBP in kerosene; viz., vapour pressure,
solubility and density and the degradation products solution of TBP in kerosene at different
temperatures in TBP-diluent-nitric acid system.

2.4 Studies on Third Phase Behaviour for TBP-Nitric Acid System


Rao and Srinivasan [42] had measured the conductivity of the organic phase after the
extraction of nitric acid by TBP in order to understand the mechanisms for the formation of
third phase. Rao and Srinivasan also conducted experiments with different concentrations of
nitric acid (2-14M) and TBP (20 to 90 volume %) and the experimental results indicated
that the conductivity variation of the organic phase can be correlated to the water content as
well as the species present in the organic phases. Rao and Srinivasan observed a higher
value of conductivity for third phase compared to the other two organic phases which was
observed to be formed at high nitric acid concentration (> 10M). The higher conductivity of
third phase was attributed to the movement of nitric acid in the micro-emulsion globules due
to the extraction of both nitric acid and moisture near third phase formation limit. A
thermodynamic model has also been developed for the calculation of speciation of TBPHNO3 complex. Fig. 2.7 shows variation in the conductivity of the organic phase as a
function of concentration of nitric acid aqueous phase and TBP. It is noticed that for a given
TBP concentration the plot of conductivity versus nitric acid concentration in the organic
phase can be classified into three portions and the transition depends upon the composition
of different species of TBP-HNO3 in the organic phase. The conductivity of organic phase

Page | 22

increases steadily with increase in acidity up to (2-8 M) (portion-1). The initial increase in
conductivity may be attributed to increased concentration of nitric acid in organic phase
leading to increased movement of charges due to percolation phenomenon. The conductivity
of organic phase nearly remains same in the second portion of the plot (8 to10 M) which
may be attributed to the percolation threshold due to formation of the reverse micelles in the
organic phase. Beyond 10 M feed nitric acid concentration (portion-3) conductivity of
organic phase increases steeply.

Rao and Srinivasan [42] also observed that (TBP)2.HNO3 concentration decreases in the
range of 2-8 M nitric acid and beyond 8 M acidity the concentration of this species in
negligible. On the other hand the concentration of TBP.HNO3 complex increases with
acidity and has maximum at about 8 M acidity and then decreases drastically beyond 9 M.
whereas, concentration of TBP.2HNO3 in the organic phase remains small and increases
drastically beyond 9 M acidity. This increased concentration of TBP.2HNO3 indicates that
micro-structure of micro-emulsion globule is changed drastically, hence more nitric acid get
extracted beyond 10 M in aqueous solution.

Comparison of concentration of the (TBP.HNO3)2, TBP.HNO3 and TBP.2HNO3 in organic


for 1.09 M and 2.18 M TBP indicates that the concentrations of all these species are higher
in 2.18 M TBP. In view of this increased concentration of these species in the organic phase
it is expected that the probability of charges movement in the micro-emulsion globules
should be higher when the TBP concentration is high.

Page | 23

Fig. 2.7 Variation of organic phase conductivity as the function of concentration of feed nitric
acid and TBP [42].

The study of Rao and Srinivasan [42] for the extraction of nitric acid using TBP indicates
that the different species are present in the extract (organic phase). Concentration of these
species changes as a function of feed acidity as well as the concentration of TBP changes in
the organic phase. Soluble water content in the organic phase decrease with increase in acid
to certain value and then increases beyond a certain limit where the formation of the third
phase takes place. Complex of TBP-HNO3 and moisture in the organic phase is employed
for explaining the variation of conductivity of the organic phase, but in this study no third
phase formation is about to take place because the concentration of nitric acid was very
much lower than 10 M and was within 2.5-3 M.

Page | 24

2.5 Thermodynamics of Extraction of Nitric Acid by Using TBP Solution


The distribution of HNO3 of initial concentration 0-8 M with TBP of concentration 5-100
volume% (in Amsco 125-82, a hydrocarbon) was measured by Davis [43]. He had arbitrarily
chosen the initial concentration of nitric acid within 0-8 M because of uncertainties in HNO3
activity coefficients in TBP diluted in Amsco are accurately described by the equation
logHNO3,org /{HNO3,aq (3.75493-(HNO3,org )} = A+ B (HNO3,org ,) where subscripts org and
aqueous refer to organic and aqueous phases.

Codding et al. [44] proposed an antilogarithms to find the constants A for TBP solution of
six different concentrations and described it as a linear function of (YH2O + YTBP), the sum of
the mole fractions, YH2O and YTBP of water and TBP in the acid-free water-saturated organic
phase. Codding et al. interpreted antilogarithms as the product KIYT, where K1 is the
thermodynamic equilibrium constant for the extraction reaction and TN was the mean
activity coefficient of TBP and TBP.H2O in the acid-free, water-saturated organic phase. As
the concentration of TBP in Amsco 125-82 increases from 0 to 100%, KIYT, in molal units,
varies from 0.2 to 1.5. The value of B in the equation is proportional to (YH2O + YTBP)1/2
while the product-B(HNO3,org ,) is interpreted as logTN, where, TN is the mean activity
coefficient of the species TBP.HNO3 and TBP.HNO3.H2O. The organic phase water and
acidity values are consistent with formation of the complexes TBP.H2O, TBP.HNO3,
TBP.HNO3.H2O, and TBP.2HNO3.

Codding et al. [44] also found that the complexities of the multicomponent solutions were
so great that no serious efforts had been made to provide quantitative interpretations.
Instead, there was a concerted effort to obtain a quantitative description of solvent extraction
Page | 25

system, viz., TBP-diluent-HNO3-H2O. With some exceptions these studies were further
simplified by elimination of the diluent, data on HNO3 extraction by TBP have been
interpreted in terms of the formation in the organic phase of a series of addition compounds,
the quantity of each changing as the aqueous nitric acid concentration changes. Thus in
absence of HNO3 the compound TBP.H2O is formed; as the aqueous HNO3 concentration
increases to 15 M, it was postulated that compounds such as TBP.HNO3, TBP.HNO3.H2O,
TBP.2HNO3, TBP.3HNO3 and TBP.4HNO3 were formed successively, although evidence
for complexes containing more than 2 moles of HNO3 per mole of TBP is very sketchy. The
study of Codding et al. for the extraction of nitric acid was limited to the regions of aqueous
acidity, primarily 5 M or less, that are normally used in the pilot plant and production
facilities. Codding et al. had performed experiments with 5 to 100 volume % solutions of
TBP in the diluent; Amsco 125-82 which is an odourless mineral spirits.

Technical grade tri-butyl phosphate and Amsco 125-82 were used as starting materials. The
TBP was partially purified (free of acid) by two or three contacts with equal volumes of
2.5% aqueous sodium carbonate; any traces of the latter were removed with three equal
volume distilled water washes. Before being stored, the resulting TBP was degassed and
dehydrated under vacuum to a water content of 1.8 mg/ml. Diluent was used after two or
three water washes.

TBP-Amsco stock solutions were synthesized by weight and then vigorously agitated in 2550 ml portions, with equal volumes of the various HNO3 solutions for 5-20 min. These
mixtures were allowed to settle until the two phases appeared to be water clear, the
minimum settling time being 15 min. and the maximum 3 days. After separation of the two
phases density, acidity, and, in some cases, nitrate were determined in the aqueous phase

Page | 26

and density, water content, acidity, and, in some case, nitrate in the organic phases.
Densities were determined with 10 ml Pycnometer, usually at 25C. Acidity was determined
by electrometric titration with appropriate sodium hydroxide solutions. Water was added to
the organic samples to make their titrations in essentially aqueous media. Water in the
organic solutions was determined by the Karl Fisher method as described by Kelley et al
[45].

Taras [46] determined nitrate by reaction with 2, 6-dimethylphenol and subsequent


colorimetric measurement in a manner similar to the method based on phenol-di-sulfonic
acid. The limit of detection of nitrate in the TBP-Amsco solutions was approximately 5 g.

Taras has listed the analytical data for the extraction of nitric acid by 5, 10, 15, 30, and 65
volume % solutions of TBP in Amsco 125-82 and by diluent-free, i.e., 100 volume %, TBP.
In addition to analytical data there are included values of the mean molar stochiometric
activity coefficients of nitric acid in water calculated from the 250C molal data of
Hartmann and Rosenfeld. Some of the extraction results were not used in the mathematical
analyses mentioned here; either because differences between nitrate and acidity
determinations, in the low-acidity region in the organic phase were large enough to suggest
the presence of other acids, perhaps di-butyl-phosphoric, or because adequate nitric acid
activity coefficient data are not available. Reichardt and Welton [47] corrected the activity
coefficients they calculated from their freezing point measurements to values at 250C only
at concentrations up to 3 M.

The mathematical description based on the extraction of nitric acid by TBP solutions
according to the reaction is shown in Eq. (9).

Page | 27

HNO3aq + TBPorg TBP. HNO3 org

(9)

From which is formulated the equilibrium constant (K1 ) as shown in Eq. (10).
K1 = C

CTBP.HNO3,org

(10)

HNO3,aq .CTBPorg

Alcock et al. [48] interpreted two different concepts for the data on the extraction of nitric
acid by TBP-diluent solutions. The first interpretation postulates much of the deviation of
the system from ideality to changes in activity coefficients of species in the organic phase as
well as in the aqueous phase. The second interpretation postulates the formation of
complexes of the type TBP.2HNO3, TBP.3HNO3, and TBP.4HNO3, in addition to
complexes such as TBP.H2O, TBP.HNO3, and TBP.HNO3.H2O, without consideration of
changes in activity coefficients.

The relation between H2O concentration and HNO3 concentration in the organic phase at
low values of concentration is shown in Eq. (11).

HNO3aq + TBP. H2 Oorg HNO3 . TBP. H2 Oorg

(11)

HNO3aq + TBP. H2 Oorg TBP. HNO3 + H2 Oaq

(12)

However, as the TBP concentration in the diluent increases, Reactions (9) and (11) become
less important while Reaction (12) becomes predominant.

Page | 28

All the above mentioned investigators [43-47] had focused mainly on why the extraction of
nitric acid with TBP in presence of metal nitrates increases but the exact data and how the
distribution coefficient of nitric acid varies with the presence of these metal nitrates is not
available and also the complex formation with TBP-Water-Nitric acid system is not given.
They have also focused on solubility of TBP in water or in presence of extractable like
uranium nitrate and plutonium nitrates. However, no literature is available on the extraction
of nitric acid by TBP in different concentrations of nitric acid in presence of different
inextractable metal nitrates. Sodium nitrate and calcium nitrate are not extracted by TBP in
PUREX process. Hence, it is informative to know the effect of these inextractable metal
nitrates on the extraction of nitric acid by TBP and distribution ratio value Kd of nitric acid.

Although a number of studies have been carried out on extraction of nitric acid by TBP, in
presence of nitrates but the reported results are rare and extraction data is not available.
Hence, the main objective of this research work is to study the extraction of nitric acid by
TBP- kerosene system in presence of nitrate ions.

2.6 Effect of Inextractable Nitrate on Solubility of TBP in Water


It was found that during the solvent extraction process, some amount of TBP gets
transferred into the aqueous acidic solutions containing dissolved metal nitrates which lead
to many environmental problems. The solubility of TBP in the aqueous solution decreases
when inorganic solutes are added to these solutions.

The presence of sodium nitrate has affected solubility of TBP in water. It was observed that
the solubility of TBP decreases with increase in the concentration of sodium nitrate from

Page | 29

0.3-3.0 mol/l i.e., 26-255 g/l in water. The salting coefficient and activity coefficient for
TBP in different concentration of sodium nitrate was calculated using Setschenow equation
[33] and the values obtained are summarized in Table 2.2. It was found that the salting
coefficient and activity coefficient values increases with the concentration of sodium nitrate
in water. Sodium nitrate is an electrolyte which acts as a salting agent by limiting the
solubility of TBP in water.

Higgins et al. [34] have also observed similar salting out of TBP in presence of different
electrolytes. Metal nitrates exert pressure on the water and thereby affects the solubility of
TBP. Schulz et al. [30] have also stated that solubility of TBP in the aqueous phase
decreases when inorganic solutes are added to water. Sodium nitrate affects the hydration
sphere of water and increases the disorder in the water system, thereby reducing the
solubility of TBP in water. Burger and Forsman [33] have also mentioned in their report that
the presence of salts in the aqueous phase decreases the solubility of TBP.

Significant works on the extraction of nitric acid from effluent are reported in literature. Few
attempts were made for the recovery of nitric acid from effluent by extracting with dilute
TBP solution. However, in literature very few information are available on the effect of the
presence of various metal nitrates on the extraction of nitric acid by using dilute TBP
solution. In the present study, experiments were carried out for the recovery of nitric acid for
reuse from the acidic solution so that total nitrate concentration of the effluent is reduced.
The experimental details and results are discussed in this thesis.

Page | 30

Table 2.2 Effect of sodium nitrate on the solubility of TBP in aqueous phase.

Conc. of

Conc. of

Solubility of

Activity

Salting

NaNO3 in

NaNO3 in

TBP, S

coefficient

Coefficient

water

water

[mg/l]

= So/S *

Ks

[mol/l]

[g/l]

[-]

[-]

0.3

26

357

1.10

0.14

0.5

43

313

1.26

0.20

1.0

85

233

1.69

0.23

1.5

128

177

2.22

0.23

2.0

170

128

3.07

0.24

2.5

213

94

4.18

0.25

3.0

255

63

6.24

0.27

*S is the solubility of TBP in sodium nitrate solutions and So is the solubility of TBP in
water; which is 393 ppm at 25oC.

Page | 31

Chapter 3

Experimental Study

3.1 Brief Process Description


The aqueous acidic solution that generated after the solvent extraction followed by UNR
treatment with treated solvent contains free nitric acid of concentration in the range of 2.5-3
N and nitrate ions (of Mg, Na, Ca, Fe etc.) of about 50-60 g/l. It is proposed to recover free
nitric acid for its reuse from the acidic solution. Tri-n-Butyl Phosphate (TBP) diluted with
an inert n-paraffin mixture is widely used as an extractant [1]. TBP is generally used in
conjunction with a hydrocarbon diluent which is inert in nature. The diluent like ndodecane, liquid paraffin, kerosene etc. improves the physical properties of TBP by
lowering the density and viscosity for better phase separation and reduces the pumping cost.

3.2 Methodology
Extensive literature review were carried out on the recovery of nitric acid from different
sources using Try-n-butyl phosphate and study the different solvents to extract and
processes to be used to recover nitric acid in presence of different metal nitrates. In the
present study Tri-n-butyl phosphate was used as extractant to recover nitric acid in absence
of nitrate ions and in presence of different concentration of nitrate ions of Na, Ca, Mg and
Al metals. The experimental studies include the following thirteen major parts as follows.
i)

Extraction of 1-4 M nitric acid solution with TBP without any nitrates.

Page | 32

ii)

Extraction of 1-4 M nitric acid solution with TBP in presence of 20 g/l NaNO3.

iii)

Extraction of 1-4 M nitric acid solution with TBP in presence of 20 g/l Ca(NO3)2.

iv)

Extraction of 1-4 M nitric acid solution with TBP in presence of 20 g/l Mg(NO3)2.

v)

Extraction of 1-4 M nitric acid solution with TBP in presence of 20 g/l Al(NO3)3.

vi)

Extraction of 1-4 M nitric acid solution with TBP in presence of 10 g/l NaNO3.

vii) Extraction of 1-4 M nitric acid solution with TBP in presence of 10 g/l Ca(NO3)2.
viii) Extraction of 1-4 M nitric acid solution with TBP in presence of 10 g/l Mg(NO3)2.
ix)

Extraction of 1-4 M nitric acid solution with TBP in presence of 10 g/l Al(NO3)3.

x)

Extraction of 1-4 M nitric acid solution with TBP in presence of 30 g/l NaNO3.

xi)

Extraction of 1-4 M nitric acid solution with TBP in presence of 30 g/l Ca(NO3)2.

xii) Extraction of 1-4 M nitric acid solution with TBP in presence of 30 g/l Mg(NO3)2.
xiii) Extraction of 1-4 M nitric acid solution with TBP in presence of 30 g/l Al(NO3)3.

3.3 Experimental Setup


The snapshot of the experimental setup is shown in Fig. 3.1. The apparatus used for
experiment are as noted below.
(i)

Pyrex Beaker of 500 ml capacity

2 nos.

(ii)

Separating funnel of 1000 ml capacity

1 no.

(iii)

Funnel

2 nos.

(iv)

Measuring cylinder of 500 ml capacity

4 nos.

(v)

Flat bottom flask of 500 ml capacity

2 nos.

(vi)

Burette

1 no.

Page | 33

All the reagents used in this work are listed in Section 3.4. Solid reagents were used to make
stock solutions by dissolving the appropriate mass of salt in purified water in a volumetric
flask. Stock solutions from liquid reagents were prepared by volume present by using
graduated cylinders and volumetric flasks.

3.4 Chemicals & Reagents


a) TBP of 98.5% purity
b) Nitric acid of industrial grade (12N)
c)

Kerosene of commercial grade (density: 0.78gm/cm3 , viscosity: 1.9 CP at 30oC).

d) Sodium nitrate,

e)

Calcium nitrate

f)

Magnesium nitrate }

All of analytical Grade and SD Fine Chemicals make,


were used.

g) Aluminium Nitrate }
In all the experiments 1:1 volume ratio of organic to aqueous phase (O/A) were used.

Fig. 3.1 A snapshot of the experimental setup.

Page | 34

3.5 Experiments
Studies were performed under a range of conditions to investigate the extraction of nitric
acid into TBP. These metal nitrates were selected for the present experimental studies;
because they are commonly used in chemical, metallurgical and nuclear industries and are
easily available and as a result generally present in effluent containing free nitric acid. The
experiments can be categorized into thirteen sets as mentioned in methodology, First set of
experiments were carried out with different concentrations of nitric acid; variedbetween14M and with 30-80 volume % TBP solution in kerosene. A second set of experiments were
performed in presence of sodium nitrate in aqueous phase with concentration of 20 g/l.
Third set of experiments were carried out in presence of calcium nitrate in aqueous phase
with concentration of 20 g/l. Fourth set of experiments were carried out in presence of
Magnesium nitrate in aqueous phase with concentration of 20 g/l. Fifth sets of experiments
were carried out in presence of 20 g/l aluminium nitrate in aqueous phase.
The similar processes were followed for the experiments with 10 g/l and 30 g/l of all metal
nitrate ions as discussed above.

3.6 Experimental Procedure


The following process steps were followed
Steps;
1.

Preparation of 100ml of 30 volume % TBP-kerosene solution.

i)

100% TBP = 0.3X100 ml = 30 ml

ii) 100% kerosene = 0.6X100 ml =60 ml

Page | 35

2. Preparation of 100ml of aqueous acidic solution of 1M nitric acid concentration with


DM water.

Industrial grade 12N nitric acid was used to make 1M concentration of nitric acid
solution. The required volume of Industrial grade 12N nitric acid was calculated by
normality equation. Where V1 = N2V2/N1 = 1X100/12 = 8.333 ml.
This amount of nitric acid was added in DM water to make the 100ml of solution.

3. Solvent Extraction

The solutions were then transferred into the separating funnel after washing the funnel
with service water. The solutions are mixed manually for 1 minute (minimum mixing
time require to reach equilibrium is 0.5 min. as mentioned in section 2.0.1) and
allowed to settle until both the phases are clearly separated.

4. Procedure of the calculation of Kd value calculation


After the extraction, raffinate solution from the separation funnel were analysed by
titration to find out the normality of remaining nitric acid in raffinate phase and the
nitric acid concentration in extract phase were determined by subtracting the raffinate
nitric acid concentration from initial nitric acid concentration.

Kd =

nitric acid in extract phase


nitric acid in raffinate phase

Page | 36

Samples were taken from the aqueous (lower) phase after clear separation of aqueous and
organic phases. Sample solutions were collected from the bottom portion in to the properly
washed and cleaned sample bottle and analysed for the normality by the titration method.
Titration with a strong base was used to determine the nitric acid concentration. Titration
was based on the concept of an equivalence point, where the concentrations of acid and base
are equal. In potentiometric titration the equivalence point occurs where the change in pH is
greatest, as plotted against the volume of base added. The true equivalence point is in an
ideal, infinitely dilute solution, and titrations actually measure the end point, the closest
approximation. During titration of a strong acid with a strong base, the endpoint should
occur at a pH of 7. Titration was done with standard 0.5804 N NaOH solution by using
Phenolphthalein as an indicator. The colour change at end point observed was from
colourless to pale pink. Results are discussed in chapter 4.
100 ml of 30% TBP in kerosene was used to extract nitric acid from aqueous solution in the
experiments. Concentrations of nitric acid used were as 1 M, 2 M, 3 M and 4 M. Same
procedures were followed for 40%, 50% 60% 70% and 80% (volume %) TBP diluted with
kerosene and distribution coefficient of nitric acid was determined.

Demineralized (DM) water was used for the stripping of nitric acid from organic phase in
presence of different metal nitrates viz., NaNO3, Ca(NO3)2, Mg(NO3)2, and Al(NO3)3.
Experiments were carried out with different concentrations of TBP and DM water with the
O/A ratio of 1:1 for a constant mixing time of 2 min. The concentration of nitric acid was
varied from 1-4 M for a particular TBP concentration and the average value of four results
of each concentration of TBP was considered for the analysis of the percentage recovery

Page | 37

from the results. Each experiment was repeated at least two times to see the reproducibility
of results.

Page | 38

Chapter 4

Results and Discussions

4.1 First Set of Experiments in Absence of Metal Nitrates


The experimental results for the extraction of nitric acid in absence of metal nitrates were
carried out with 30-80% TBP in kerosene are shown in Tables 4.1-4.6.Initial concentration
of nitric acid was varied from 1 to 4 M and each set of experiments were repeated at least
two times. The reproducibility of the results was within 1%. Equilibrium concentration of
nitric acid in raffinate after extraction was determined by titration. Tables 4.1-4.6 show the
average value of results in both aqueous and organic phases.
Table 4.1 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and organic
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[volume %]

Initial HNO3
concentration [M]

Concentration of HNO3
in raffinate [M]

K d (org./aq.)
[-]

30

0.810

0.230

30

1.650

0.212

30

2.520

0.191

30

3.420

0.170

Table 4.2 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and organic
phase, nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[volume %]
40
40
40
40

Initial HNO3
concentration [M]
1
2
3
4

Concentration of
HNO3in raffinate [M]
0.760
1.560
2.410
3.268

K d (org./aq)
[-]
0.316
0.282
0.245
0.224

Page | 39

Table 4.3 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and organic
phase, nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP

Initial HNO3

Concentration of HNO3

[volume %]

concentration [M]

in raffinate [M]

K d (org./aq)
[-]

50

0.740

0.351

50

1.500

0.333

50

2.300

0.304

50

3.100

0.290

Table 4.4 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and organic
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP

Initial HNO3

Concentration of

[volume %]

concentration [M]

HNO3 in raffinate [M]

K d (org./aq)
[-]

60

0.710

0.408

60

1.430

0.400

60

2.175

0.380

60

2.915

0.372

Table 4.5 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and organic
phase, nitric acid was extractedby using 70% TBP (diluted with kerosene).

TBP

Initial HNO3

Concentration of

[volume %]

concentration [M]

HNO3 in raffinate [M]

K d (org./aq)
[-]

70

0.680

0.470

70

1.380

0.449

70

2.080

0.442

70

2.793

0.432

Page | 40

Table 4.6 Equilibrium concentration of nitric acid in absence of metal nitraes in aqueos and organic
phase, nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP
[volume %]
80

0.650

0.538

80

1.300

0.538

80

1.980

0.515

80

2.668

0.499

1.4

HNO3 concentration in extract phase [mol/l]

Concentration of
K d (org./aq)
HNO3 in raffinate [M]
[-]

Initial HNO3
concentration [M]

30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.2

1.0

0.8

0.6

0.4

0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]

Fig. 4.1 The extraction of nitric acid in the range of (14M) by various concentration of tri-butyl
phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A = 1) and at 25C was
determined in the absence of nitrate ions

Page | 41

The equilibrium curve of nitric acid in organic and aqueous phase is shown in Fig. 4.1. It
was found that the concentration of nitric acid in the organic phase increases with increase
in the concentration of nitric acid in the aqueous phase.

HNO3 concentration in extract phase [mol/l]

1.4

1 M Nitric acid
2 M Nitric acid
3 M Nitric acid
4 M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.2 Variation of nitric acid concentration in organic phase with TBP concentration (30%80%) in the absence of nitrates ion.

Variation of nitric acid concentration in organic phase with TBP concentration (30-80
volume %) in the absence of nitrates in the first set of experiments is shown in Fig. 4.2. It
was observed that the percentage extraction of nitric acid increases from 14.5 33.3% (Kd=
0.170.499) as the TBP concentration varies from 30 80 volume percentage in a single
stage extraction.

Page | 42

The variation of the concentration of nitric acid in the extract with the initial concentration
of nitric acid in aqueous phase is shown in Fig. 4.3. It was found that the concentration of
nitric acid in the organic phase increases with increasing the concentration of nitric acid in
the aqueous phase. As given in literature section 2.0.2 the nitric acid concentration in extract
phase for 2 M initial nitric acid concentration is 0.165 M extracted by 0.367 M (10 volume
%) in kerosene. As shown in Fig. 4.3 nitric acid concentration in extract phase increase up

HNO3 concentration in extract phase (mol/l)

to 0.35 M if extracted by 1.095 M (30 volume %) TBP diluted by kerosene.

1.095 M of TBP
diluted in kerosene.
(30 volume %)

0.6

0.5

0.4

0.3

0.2
1.0

1.5

2.0

2.5

3.0

3.5

4.0

Initial HNO3 conc. in aqueous phase (mol/l)


Fig. 4.3 The variation of the nitric acid concentration in the extract with the initial
concentration of nitric acid in aqueous phase; which was varied from 14 M. 1.095 M (30
volume %) TBP diluted with kerosene was used for the extraction with O/A= 1 and extractions
were carried out at 25C.

Page | 43

4.2 Second Set of Experiments in Presence of 20 g/l Sodium Nitrate


The experimental results for the experiments for the extraction of nitric acid in presence of
20 g/l sodium nitrate; carried out with 30-80 volume % TBP in kerosene are shown in
Tables 4.7-4.12. Initial concentration of nitric acid was varied from 1 to 4 M and each set of
experiments were repeated at least two times. The reproducibility of the results was within
1%. Equilibrium concentration of nitric acid in raffinate after extraction was determined by
titration. Tables 4.7-4.12 show the average values of results in both aqueous and organic
phases.

Table 4.7 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[volume %]

HNO3 with 20 g/l


NaNO3 [M]

Concentration of HNO3 in
raffinate [M]

K d (org./aq.)
[-]

30

0.800

0.250

30

1.630

0.227

30

2.458

0.220

30

3.325

0.203

Table 4.8 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of HNO3

[volume %]

NaNO3 [M]

in raffinate [M]

K d (org./aq.)
[-]

40

0.758

0.319

40

1.540

0.298

40

2.330

0.287

40

3.154

0.268

Page | 44

Table 4.9 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of HNO3

[volume %]

NaNO3 [M]

in raffinate [M]

K d (org./aq.)
[-]

50

0.723

0.383

50

1.470

0.361

50

2.220

0.351

50

3.000

0.333

Table 4.10 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP
[volume %]
60
60
60
60

HNO3 with 20 g/l


NaNO3 [M]
1
2
3
4

Concentration of HNO3
in raffinate [M]
0.682
1.405
2.118
2.856

K d (org./aq.)
[-]
0.466
0.423
0.416
0.401

Table 4.11 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

TBP
[volume %]
70

HNO3 with 20
g/l NaNO3 [M]
1

Concentration of HNO3
in raffinate [M]
0.642

K d (org./aq.)
[-]
0.557

70

1.330

0.503

70

2.000

0.500

70

2.725

0.468

Page | 45

Table 4.12 Equilibrium concentration of nitric acid in presence of 20 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP
[volume %]
80
80
80
80

HNO3 with 20 g/l


NaNO3 [M]
1
2
3
4

Concentration of HNO3 in
raffinate [M]
0.610
1.252
1.880
2.570

K d (org./aq.)
[-]
0.639
0.597
0.596
0.556

HNO3 concentration in extract phase [mol/l]

1.6

30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in presence of 20 g/l NaNO3

Fig. 4.4 The extraction of nitric acid in the range of (14 M) by various concentration of tributyl phosphate/kerosene (30% - 80%) at an organic to aqueous phase ratio (O/A= 1), and at
25C was determined in presence of 20 g/l NaNO3.

The variations of the equilibrium concentration of nitric acid in aqueous and organic phase
for different concentration of TBP in kerosene are shown in Fig. 4.4. It was found that the

Page | 46

concentration of nitric acid in the organic phase increases due to the presence of NaNO3 in

aqueous phase. It was also found that as the concentration of TBP in kerosene (organic
phase) increases the equilibrium concentration of nitric acid in organic phase increases.

For the second set of experiments, the variation of nitric acid concentration in organic phase
with TBP concentration in presence of 20 g/l sodium nitrates in aqueous phase at the
beginning is shown in Fig. 4.5 It was observed that the percentage extraction of nitric acid
increases from 16.88 35.75% (Kd= 0.2030.556) as the TBP concentration varies from 30
80 volume percent in a single stage extraction in presence of 20 g/l NaNO3 in feed
solution.

HNO3 concentration in extract phase [mol/l]

1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.5 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/l sodium nitrates.

Page | 47

4.3 Third Set of Experiments in Presence of 20 g/l Calcium Nitrate


The experimental results for the extraction of nitric acid in presence of 20 g/l calcium nitrate
in feed solution, carried out with 30-80 volume % TBP in kerosene are shown in Tables
4.13-4.18. Initial concentration of nitric acid was varied from 1 to 4 M and each set of
experiments were repeated at least two times. The reproducibility of the results was within
1%. Equilibrium concentration of nitric acid in raffinate after extraction was determined by
titration. Tables 4.13-4.18 show the average value of results in both phases.

Table 4.13 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[Volume %]

HNO3 with 20 g/l


Ca(NO3)2 [M]

30

30

Concentration of HNO3 K d (org./aq.)


in raffinate [M]
[-]
0.799

0.251

1.636

0.222

30

2.461

0.219

30

3.337

0.200

Table 4.14 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[Volume %]

HNO3 with 20 g/l


Ca(NO3)2 [M]

40
40
40
40

1
2
3
4

Concentration of HNO3 K d (org./aq.)


in raffinate [M]
[-]
0.760
1.532
2.335
3.168

0.316
0.305
0.284
0.263

Page | 48

Table 4.15 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

[Volume %]

Ca(NO3)2 [M]

50

Concentration of HNO3 K d (org./aq.)


in raffinate [M]

[-]

0.724

0.381

50

1.470

0.361

50

2.215

0.354

50

2.997

0.335

Table 4.16 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

[Volume %]

Ca(NO3)2 [M]

60

Concentration of HNO3 K d (org./aq.)


in raffinate [M]

[-]

0.688

0.453

60

1.390

0.439

60

2.110

0.421

60

2.835

0.411

Table 4.17 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

[Volume %]

Ca(NO3)2 [M]

70

Concentration of HNO3 K d (org./aq.)


in raffinate [M]

[-]

0.654

0.529

70

1.330

0.504

70

1.985

0.511

70

2.710

0.476

Page | 49

Table 4.18 Equilibrium concentration of nitric acid in presence of 20 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of

Kd(org./aq.)

[Volume %]

Ca(NO3)2 [M]

HNO3 in raffinate [M]

[-]

80

0.615

0.626

80

1.245

0.606

80

1.901

0.578

80

2.574

0.554

HNO3 concentration in extract phase [mol/l]

1.6

30% TBP
40% TBP
50% TBP
60% TBP
70% TBP
80% TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in presence of 20 g/l Ca(NO3)2
Fig. 4.6 The extraction of nitric acid in the range of (14 M) by various concentration of tri-butyl
phosphate/kerosene (30% - 80%) at an organic to aqueous phase ratio (O/A= 1), and at 25C was
determined in presence of 20 g/l Ca(NO3)2.

The variation equilibrium concentrations of nitric acid in aqueous and organic phase are
shown in Fig. 4.6. It was found that the concentration of nitric acid in the organic phase
Page | 50

increases with increasing the concentration of nitric acid in the aqueous phase. It was also
observed that these results are almost similar as found in the presence of 20 g/l NaNO3.

Experimental result for the third set of experiments i.e., variation of nitric acid concentration
inorganic phase with the TBP concentration in organic phase and feed contains 20 g /l
calcium nitrate are shown in Fig. 4.7 It was observed that the percentage extraction of nitric
acid increases from 16.57 35.64% (Kd= 0.1980.55) as the TBP concentration varies from
30 80 volume percentage in single stage extraction.

HNO3 concentration in extract phase [mol/l]

1.4

1 M Nitric acid
2 M Nitric acid
3 M Nitric acid
4 M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.7 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/l calcium nitrates.

Page | 51

4.4 Forth Set of Experiments in Presence of 20 g/l Magnesium Nitrate


The experimental results for the extraction of nitric acid in presence of 20 g/l magnesium
nitrate; carried out with 30-80 volume % TBP in kerosene are shown in Tables 4.19-4.24.
Initial concentrations of nitric acid in feed solution were varied from 1 to 4 M and each set
of experiments were repeated for at least two times. The reproducibility of the results was
within 1%. Equilibrium concentration of nitric acid in raffinate after extraction was
determined by titration. Tables 4.19-4.24 show the average value of results in both phases.

Table 4.19 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[Volume %]

Concentration of
HNO3 in raffinate [M]

Kd (org./aq.)
[-]

30

HNO3 with 20 g/l


Mg(NO3)2
[M]
1

0.786

0.271

30

1.609

0.242

30

2.426

0.236

30

3.266

0.225

Table 4.20 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[Volume %]

Concentration of
HNO3 in raffinate [M]

Kd(org./aq.)
[-]

40

HNO3 with 20 g/l


Mg(NO3)2
[M]
1

0.753

0.328

40

1.514

0.321

40

2.285

0.313

40

3.100

0.290

Page | 52

Table 4.21 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of

Kd(org./aq.)

[Volume %]

Mg(NO3)2

HNO3 in raffinate

[-]

[M]

[M]

50

0.717

0.395

50

1.450

0.380

50

2.190

0.367

50

2.950

0.357

Table 4.22 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of

Kd(org./aq.)

[Volume %]

Mg(NO3)2

HNO3 in raffinate

[-]

[M]

[M]

60

0.682

0.466

60

1.387

0.442

60

2.080

0.442

60

2.805

0.426

Table 4.23 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted kerosene).

TBP

HNO3 with 20 g/l

Concentration of

Kd (org./aq.)

[Volume %]

Mg(NO3)2

HNO3 in raffinate [M]

[-]

[M]
70

0.642

0.557

70

1.305

0.533

70

1.962

0.529

70

2.690

0.487

Page | 53

Table 4.24 Equilibrium concentration of nitric acid in presence of 20 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP
[Volume %]
80

HNO3 with 20 g/l


Mg(NO3)2
[M]
1

80

Concentration of HNO3 Kd(org./aq.)


in raffinate [M]
[-]
0.608

0.645

1.226

0.630

80

1.856

0.616

80

2.540

0.574

Fig. 4.8 shows the variation of equilibrium concentrations of nitric acid in organic phase
with that in aqueous phase; for different initial concentrations of TBP in organic phase. It
was found that the concentration of nitric acid in the organic phase increases in presence of
20 g/l Mg(NO3)2 as compared that in presence of NaNO3 and Ca(NO3)2 individually.
Moreover, like previous experiments the equilibrium concentration of nitric acid in organic
phase increases with increase in the initial concentration of TBP in organic phase as shown
in Fig. 4.8.

Experimental results of the fourth set of experiments are shown in Fig. 4.9, which shows the
variation of nitric acid concentration in organic phase with TBP concentration in presence of
20 g/l Magnesium nitrates. It was observed that the percentage extraction of nitric acid
increases from18.35 36.50 % (Kd = 0.2240.574) as the concentration of TBP increases
from 30 80 volume percentage in a single stage extraction.

Page | 54

HNO3 concentration in extract phase [mol/l]

1.6
1.4

30% TBP
40% TBP
50% TBP
60% TBP
70% TBP
80% TBP

1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in presence of 20 g/l Mg(NO3)2

Fig. 4.8 The extraction of nitric acid in the range of (14 M) by various concentration of tri-butyl
phosphate/kerosene (30 80 %) at an organic to aqueous phase ratio (O/A= 1), and at 25C was
determined in presence of 20 g/l Mg(NO3)2.

HNO3 concentration in extract phase [mol/l]

1.4

1 M Nitric acid
2 M Nitric acid
3 M Nitric acid
4 M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume % ]

Fig. 4.9 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/l Magnesium nitrates.

Page | 55

4.5 Fifth Set of Experiments in Presence of 20 g/l Aluminium Nitrate


The experimental results for the extraction of nitric acid in presence of 20 g/l Aluminium
nitrate were carried out with 30-80 volume % TBP in kerosene are shown in Tables 4.254.30. Initial concentration of nitric acid was varied from 1 to 4 M and each set of
experiments were repeated at least two times. The reproducibility of the results was within
1%. Equilibrium concentration of nitric acid in raffinate after extraction was determined by
titration. Tables 4.25-4.30 show the average value of results in both aqueous and organic
phases.
Table 4.25 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of

Kd (org./aq.)

[Volume %]

Al(NO3)3

HNO3 in raffinate

[-]

[M]

[M]

30

0.764

0.309

30

1.552

0.289

30

2.341

0.281

30

3.160

0.266

Table 4.26 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of

[Volume %]

Al(NO3)3[M]

HNO3 in raffinate

Kd(org./aq.)
[-]

[M]
40

0.733

0.363

40

1.478

0.353

40

2.235

0.342

40

3.009

0.329

Page | 56

Table 4.27 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of

Kd

[Volume %]

Al(NO3)3

HNO3 in

(org./aq.)

[M]

raffinate [M]

[-]

50

0.703

0.422

50

1.428

0.401

50

2.130

0.408

50

2.887

0.386

Table 4.28 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP

HNO3 with 20

Concentration of

Kd(org./aq.)

[Volume %]

g/lAl(NO3)3

HNO3 in raffinate

[-]

[M]

[M]

60

0.667

0.499

60

1.358

0.473

60

2.051

0.462

60

2.766

0.446

Table 4.29 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

TBP

HNO3 with 20 g/l

Concentration of

Kd (org./aq.)

[Volume %]

Al(NO3)3

HNO3 in raffinate

[M]

[M]

70

0.624

0.603

70

1.276

0.568

70

1.938

0.548

70

2.648

0.511

[-]

Page | 57

Table 4.30 Equilibrium concentration of nitric acid in presence of 20 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP
[Volume %]
80

HNO3 with 20 g/l


Al(NO3)3
[M]
1

Concentration of
HNO3 in raffinate
[M]
0.584

Kd (org./aq.)
[-]

80

1.197

0.671

80

1.805

0.662

80

2.491

0.605

0.712

HNO3 concentration in extract phase [mol/l]

1.8
1.6

30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in presence of 20 g/l Al(NO3)3
Fig. 4.10 The extraction of nitric acid in the range of (14 M) by various concentration of tributyl phosphate/kerosene (30% - 80%) at an organic to aqueous phase ratio (O/A= 1), and at
25C was determined in presence of 20 g/l Al(NO3)3.

The equilibrium concentration of nitric acid in aqueous and organic phase was plotted as
shown in Fig. 4.10. The concentration of nitric acid in the organic phase increases in
presence of 20 g/l Al(NO3)3 as compared that for other metal nitrates.

Page | 58

Experimental results of the fifth set of experiments for the variation of nitric acid
concentration in organic phase with TBP concentration different concentrations of nitric
acid in feed solution and in presence of 20 g/l aluminium nitrate in feed solution are shown
in Fig. 4.11. It was observed that the percentage extraction of nitric acid increases from 21.0
37.71 % (Kd= 0.2650.605) as the TBP concentration varied from 30 80 volume
percentage in kerosene in a single stage extraction.

HNO3 concentration in extract phase [mol/l]

1.6

1 M Nitric acid
2 M Nitric acid
3 M Nitric acid
4 M Nitric acid

1.4
1.2
1.0
0.8
0.6
0.4
0.2
30

40

50

60

70

80

concentration of TBP in kerosene [volume %]

Fig. 4.11 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 20 g/l aluminium nitrates.

The percentage extraction was calculated with the presence of 20 g/l metal nitrates and
without nitrates, shown in Fig. 4.12 with 4M of initial concentration of nitric acid in
aqueous phase. It was observed that percentage extraction is higher in presence of
Page | 59

Al(NO3)3in which nitric acid extraction increased from 21 to 37.71% (Kd = 0.265-0.605) in
a single contact when TBP concentration increased from 30 to 80 volume %. As compare to
solution of without nitrate ions where the nitric acid extraction increased from 14.5 to 33.3%
(Kd = 0.169-0.499). Generally, the extraction of acid can be enhanced by the common-ion
effect of nitrate ions that is produced by the dissociation of the nitrates present in aqueous
solution. The cation associated with the nitrate impacts the effectiveness of the salting-out
agent. The distribution ratio increases as the ionic radius of the metal cation of the salting
agent decreases. For example the effectiveness of the salting-out agent decreases as follows:
Al(NO3)3>Mg(NO3)2>NaNO3~Ca(NO3)2.The smaller cation essentially provides free nitrate
in solution since the dissociation of the ions is greater.
Ionic radius of above metal nitrates which were used in these experiments is given in Table
4.31.
Table 4.31 Ionic radius of cation salting agents used in the experiments

Metal ions

Ionic radius [ A]

Na+

1.02

Ca+2

0.99

Mg+2

0.72

Al+3

0.535

Table 4.31 shows that Na+ and Ca+2 has nearly the same ionic radius and thats why their
presence in aqueous solution containing nitric acid shows similar results in the extraction of
nitric acid by using TBP diluted in kerosene as discussed in the above sections. It is also
found that the extraction of nitric acid increases as the ionic radius of cation of salting out
agent decreases.
Page | 60

Fig. 4.13 shows the effect of TBP concentration on the distribution coefficient of nitric acid
in the absence and presence of 20 g/l of various nitrate ions, the increase of nitric acid in
organic phase when the aqueous solution is having Al(NO3)3 confirm that the presence of
Al(NO3)3 salting out effect is more compare to other nitrates.

40

without nitrates
with NaNO3
with Mg(NO3)2
with Al(NO3)3
with Ca(NO3)2

Percentage extraction [E, %]

35

30

25

20

15
30

40

50

60

70

80

concentration of TBP in kerosene [volume %]

Fig. 4.12 Effect of extractant concentration on the extraction efficiency of HNO3 (O:A = 1, single
contact 3 min. 22C, aqueous phase; 4 M HNO3).

Page | 61

Without Nitrates
20 g/L NaNO3
20 g/L Mg(NO3)2
20 g/L Al(NO3)3

Distribution coefficient, Kd

0.6

0.5

0.4

0.3

0.2

0.1
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.13 Effect of TBP concentration on distribution coefficient of nitric acid in presence and
absence of nitrate ions (O: A = 1, single contact 3 min. 22C, aqueous phase: 4 M HNO3)

4.6 Effect of Nitrate Concentration on the Extraction of Nitric Acid


Experiments were carried out to find out the effect of nitrate ions concentration on the
extraction of 2M nitric acid by keeping TBP concentration constant. Nitrate ion
concentration was varied by changing NaNO3 concentration from 10-60 g/l in aqueous
solution and extracted with 50 volume % TBP solution diluted with kerosene. The
extraction is based on the Equations.(12-14). Fig. 4.14 is a plot based on Eq. (14) and
demonstrates the linear relationship, with a slope of 0.97319 0.0453, between acid
extraction and the nitrate ion. The details of the extraction conditions are noted in Table
4.32.

Page | 62

H++ NO3+ TBP

TBP.HNO3

(12)

. 3

+ . 3 .

Keq =

log

(13)

= log[Keq ]+log[3 ] + log[TBP ,]

(14)

Table 4.32 Detail of the Extraction data of 2M initial nitric acid solution with 50% TBP solution in
kerosene with 10-60 g/l concentration of NaNO3.

Kd

log[Kd]

10

CNO3 , M
2.117

0.351

-0.454

20

2.235

0.360

-0.443

0.349

30

2.352

0.380

-0.419

0.371

40

2.470

0.404

-0.393

0.392

50

2.588

0.423

-0.373

0.413

60

2.705

0.440

-0.356

0.432

NaNO3g/l

log[3 ]
0.325

Page | 63

-0.34
-0.36

log Kd

-0.38
-0.40
-0.42
-0.44
-0.46
0.32

0.34

0.36

0.38

0.40

0.42

0.44

log[CNO ]
3

Fig. 4.14 Effect of nitrate ion concentration on the extraction of 2M Nitric acid with 50% TBP
solution.

Experiments were carried out to find out effect of other nitrate ion concentration on the
extraction efficiency of nitric acid from aqueous solution in presence of nitrate ion of 10 and
30 g/l concentration.

4.7 Nitric Acid Extraction in Presence of 10 g/l NaNO3 by TBP Diluted with
Kerosene
The experimental results for the extraction of nitric acid in presence of 10 g/l sodium
nitrate; carried out with 30-80 volume % TBP in kerosene are shown in Tables 4.33-4.38.
Initial concentration of nitric acid was varied from 1 to 4 M and each set of experiments
were repeated at least two times. The reproducibility of the results was within 1%.
Equilibrium concentration of nitric acid in raffinate after extraction was determined by

Page | 64

titration. It may be noted that the Tables 4.33-4.38 show the average value of results in
both phases.

Table 4.33 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[ Volume %]
30
30
30
30

HNO3 with 10 g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.800
1.640
2.510
3.382

Kd
(org./aq.)
[-]
0.250
0.219
0.195
0.183

Table 4.34 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[ Volume %]
40
40
40
40

HNO3 with 10 g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.760
1.560
2.410
3.200

Kd
(org./aq.)
[-]
0.316
0.282
0.245
0.250

Table 4.35 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos phase,
nitric acid was extractedby using 50% TBP (diluted with kerosene).

TBP
[ Volume %]
50
50
50
50

HNO3 with 10 g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.723
1.480
2.245
3.045

Kd (org./aq.)
[-]
0.383
0.351
0.336
0.314

Page | 65

Table 4.36 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP

HNO3 with 10 g/l

Concentration of

Kd(org./aq.)

[ Volume %]

NaNO3

HNO3 in raffinate

[-]

[M]

[M]

60

0.680

0.471

60

1.413

0.415

60

2.120

0.415

60

2.840

0.408

Table 4.37 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

TBP

HNO3 with 10 g/l

Concentration of

Kd(org./aq.)

[ Volume %]

NaNO3

HNO3 in raffinate

[-]

[M]

[M]

70

0.646

0.548

70

1.340

0.493

70

2.020

0.485

70

2.750

0.455

Table 4.38 Equilibrium concentration of nitric acid in presence of 10 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP

HNO3 with 10 g/l

Concentration of

Kd(org./aq.)

[ Volume %]

NaNO3

HNO3 in raffinate

[-]

[M]

[M]

80

0.620

0.613

80

1.260

0.588

80

1.900

0.579

80

2.580

0.550

Page | 66

HNO3 concentration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


In the presence of 10 g/l NaNO3
Fig. 4.15 The extraction of nitric acid in the range of (14M) by various concentration of tributyl phosphate/kerosene (30% - 80%) at an organic to aqueous phase ratio (O/A= 1), and at
25C was determined in presence of 10 g/l NaNO3.

Fig 4.15 shows the change of the equilibrium concentration of nitric acid in aqueous and
organic phase in presence of 10 g/l NaNO3 in aqueous phase. The concentration of nitric
acid in the organic phase increases with increasing the concentration of nitric acid in the
aqueous phase.

Page | 67

HNO3 concentration in extract phase [mol/l]

1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.16 Variation of nitric acid concentration in organic phase with the initial concentration of
TBP in kerosene in presence of 10 g/l sodium nitrate in feed solution.

Result of sixth set of experiments are shown in Fig. 4.16, which shows the variation of nitric
acid concentration in organic phase with the initial concentration of TBP in kerosene in
presence of 10 g/l sodium nitrate in feed solution. It was observed that the percentage
extraction of nitric acid increases from15.45 35.50 % (Kd= 0.1830.550) as the initial
concentration of TBP in kerosene varies from 30 80 volume percentage in a single stage
extraction.

Page | 68

4.8 Nitric Acid Extraction in Presence of 10 g/l Ca(NO3)2 by TBP Diluted


with Kerosene
The experiments for the extraction of nitric acid in presence of 10 g/l calcium nitrate in
feed solution were carried out with 30-80 volume % TBP in kerosene and the
experimental results are shown in Tables 4.39-4.44. Initial concentration of nitric acid was
varied from 1 to 4 M and each set of experiments were repeated for at least two times. The
reproducibility of the results was within 1%. Equilibrium concentration of nitric acid in
raffinate after extraction was determined by titration. Tables 4.39-4.44 show the average
value of results in both organic and aqueous phases.

Table 4.39 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[Volume
%]
30
30
30
30

HNO3 with 10 g/l


Ca(NO3)2
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.800
1.640
2.480
3.350

K d (org./aq.)
[-]
0.250
0.219
0.209
0.194

Table 4.40 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[Volume %]
40
40
40
40

HNO3 with 10 g/l


Ca(NO3)2
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.760
1.550
2.361
3.257

K d (org./aq.)
[-]
0.316
0.290
0.271
0.228

Page | 69

Table 4.41 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

50

0.725

0.379

50

1.470

0.360

50

2.244

0.337

50

3.035

0.318

TBP
[Volume %]

[-]

Table 4.42 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

60

0.690

0.449

60

1.400

0.428

60

2.150

0.395

60

2.880

0.388

TBP
[Volume %]

[-]

Table 4.43 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

70

0.660

0.515

70

1.340

0.492

70

2.080

0.442

70

2.790

0.434

TBP
[Volume %]

[-]

Page | 70

Table 4.44 Equilibrium concentration of nitric acid in presence of 10 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

80

0.620

0.613

80

1.250

0.600

80

1.950

0.538

80

2.610

0.533

TBP
[Volume %]

[-]

Result of seventh set of experiments are shown in Fig. 4.18 which shows the variation of
nitric acid concentration in organic phase with the initial concentration of TBP in kerosene
and in presence of 10 g/l Ca(NO3)2 in feed solution. The initial concentration of nitric acid
in feed solution was varied for 1-4 M and it was observed that the percentage extraction of
nitric acid increases from16.25 34.75% (Kd= 0.1940.532) as the initial nitric acid
concentration increases in feed solution.

Fig. 4.17 shows the Variation of the equilibrium concentration of nitric acid in extract
with that in raffinate, the experiments were carried out at 25oC with O/A ration of 1:1 and
feed solution contains 10 g/l Ca(NO3)2 and with different concentration of TBP (30 80
%) in kerosene. It was found that the equilibrium concentration of nitric acid in extract
increases with increase in initial concentration of TBP in kerosene.

Page | 71

HNO3 concentration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in presence of 10 g/l Ca(NO3)2 in feed solution

Fig.4.17 Variation of the equilibrium concentration of nitric acid in extract with that in raffinate,
the experiments were carried out at 25oC with O/A ratio of 1:1 and feed solution contains 10 g/l
Ca(NO3)2 and with different concentration of TBP (30 - 80%) in kerosene.

HNO3 concentration in extract phase [mol/l]

1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2
1.0
0.8
0.6
0.4
0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.18 Variation of nitric acid concentration in organic phase with the initial concentration of
TBP in kerosene and in presence of 10 g/l Ca(NO3)2 in feed solution.

Page | 72

4.9 Nitric Acid Extraction in Presence of 10 g/l Mg(NO3)2 by TBP Diluted


with Kerosene
The experiments for the extraction of nitric acid in presence of 10 g/l magnesium nitrate in
feed solution were carried out by using 30-80 volume % TBP in kerosene. The
experimental results are shown in Tables 4.45-4.50. Initial concentration of nitric acid was
varied from 1 to 4 M and each set of experiments were repeated at least two times. The
reproducibility of the results was within 1%. Equilibrium concentration of nitric acid in
raffinate after extraction was determined by titration. Tables 4.45-4.50 show the average
value of results in both organic and aqueous phase.

Table 4.45 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[volume %]
30
30
30
30

HNO3 with 10 g/l


Mg(NO3)2
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.800
1.620
2.440
3.320

Kd (org./aq.)
[-]
0.250
0.234
0.229
0.205

Table 4.46 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[volume %]
40
40
40
40

HNO3 with 10 g/l


Mg(NO3)2
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.758
1.538
2.315
3.106

Kd(org./aq.)
[-]
0.319
0.300
0.296
0.288

Page | 73

Table 4.47 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

50

0.723

0.383

50

1.458

0.372

50

2.241

0.339

50

3.042

0.315

TBP
[volume %]

Kd(org./aq.)
[-]

Table 4.48 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

60

0.682

0.466

60

1.415

0.413

60

2.150

0.395

60

2.870

0.394

TBP
[volume %]

Kd(org./aq.)
[-]

Table 4.49 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

70

0.643

0.555

70

1.340

0.492

70

2.050

0.463

70

2.770

0.444

TBP
[volume %]

Kd(org./aq.)
[-]

Page | 74

Table 4.50 Equilibrium concentration of nitric acid in presence of 10 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

HNO3 with 10 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

80

0.617

0.620

80

1.246

0.605

80

1.880

0.595

80

2.560

0.562

TBP
[volume %]

Kd (org./aq.)
[-]

Fig. 4.19 shows the variation of the equilibrium concentration of nitric acid in extract with
that in raffinate, the experiments were carried out at 25oC with O/A ratio of 1:1 and feed
solution contains 10 g/l Mg(NO3)2 and with different concentration of TBP (30 - 80%) in
kerosene. It was found that the concentration of nitric acid in the organic phase increasing as
the initial concentration of TBP increases from 30-80 volume % in kerosene.

Experimental results of the eighth set of experiment are shown in Fig. 4.20. It was observed
that the percentage extraction of nitric acid increases from17.00 36.00 % (Kd= 0.205
0.562) as the initial concentration of TBP in kerosene varied from 3080 volume percentage
in a single stage extraction.

Page | 75

HNO3 concetration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


In the presence of 10 g/l Mg(NO3)2

Fig. 4.19 Variation of the equilibrium concentration of nitric acid in extract with that in
raffinate, the experiments were carried out at 25oC with O/A ratio of 1:1 and feed solution
contains 10 g/l Mg(NO3)2 and with different concentration of TBP (30 - 80%) in kerosene.

HNO3 concentration in extract phase [mol/l]

1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.20 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 10 g/l Magnesium nitrates.

Page | 76

4.10 Nitric Acid Extraction in Presence of 10 g/l Al(NO3)3 by TBP Diluted


with Kerosene
The experimental results for the extraction of nitric acid in presence of 10 g/l Aluminium
nitrate, carried out with 30-80 volume % TBP in kerosene are shown in Tables 4.51-4.56.
Initial concentration of nitric acid was varied from 1 to 4 M and each set of experiments
were repeated at least two times. The reproducibility of the results was within 1%.
Equilibrium concentration of nitric acid in raffinate after extraction was determined by
titration. Tables 4.51-4.56 show the average value of results in both the phases.

Table 4.51 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[volume %]
30
30
30
30

HNO3 with 10g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.773
1.560
2.380
3.200

K d (org./aq.)
[-]
0.294
0.282
0.260
0.250

Table 4.52 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[volume %]
40
40
40
40

HNO3 with 10 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of HNO3 in
raffinate
[M]
0.740
1.500
2.250
3.015

Kd
(org./aq.)
[-]
0.351
0.333
0.333
0.327

Page | 77

Table 4.53 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP
[volume %]
50
50
50
50

HNO3 with 10 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of HNO3
in raffinate
[M]
0.719
1.442
2.193
2.952

Kd
(org./aq.)
[-]
0.391
0.387
0.368
0.355

Table 4.54 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos
phase, nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP
[volume %]
60
60
60
60

HNO3 with 10 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.673
1.374
2.100
2.792

Kd
(org./aq.)
[-]
0.486
0.456
0.429
0.433

Table 4.55 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

TBP
[volume %]
70
70
70
70

HNO3 with 10
g/l Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.636
1.290
2.000
2.690

K d (org./aq.)
[-]
0.572
0.550
0.500
0.487

Table 4.56 Equilibrium concentration of nitric acid in presence of 10 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP
[volume %]
80
80
80
80

HNO3 with 10 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.600
1.210
1.830
2.500

Kd
(org./aq.)
[-]
0.666
0.653
0.639
0.600
Page | 78

The equilibrium concentration of nitric acid in aqueous and organic phase; plotted as shown
in Fig. 4.21.The concentration of nitric acid in the organic phase increasing as the TBP
concentration increase from 30-80 volume % in kerosene.

HNO3 concentration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


In the presence of 10 g/l Al(NO3)3
Fig. 4.21 The extraction of nitric acid in the range of (14 M) by different concentration of tributyl phosphate/kerosene (30 80 %) at an organic to aqueous phase ratio (O/A = 1), and
carried out at 25C was determined in presence of 10 g/l Al(NO3)3.

Experimental results for ninth set of experiments are shown in Fig. 4.22, which shows
variation of equilibrium concentration of nitric acid in organic phase with the initial
concentration of TBP in kerosene. It was observed that the percentage extraction of nitric
acid increases from 20.00 37.50% (Kd= 0.2500.600) as the nitric acid concentration of
nitric acid in feed solution TBP concentration varied from 30 80 volume percentage in a
single stage extraction.
Page | 79

HNO3 concentration in extract phase [mol/l]

1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2
1.0
0.8
0.6
0.4
0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.22 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 10 g/l Al(NO3)3.

4.11 Nitric Acid Extraction in Presence of 30 g/l NaNO3 by TBP Diluted


with Kerosene
The experimental results for the extraction of nitric acid in presence of 30 g/l sodium
nitrate, carried out with 30-80 volume % TBP in kerosene are shown in Tables 4.57-4.62.
Initial concentration of nitric acid was varied from 1 to 4 M and each set of experiments
were repeated at least two times. The reproducibility of the results was within 1%.
Equilibrium concentration of nitric acid in raffinate after extraction was determined by
titration. Tables 4.57-4.62 show the average value of results in both the phases.

Page | 80

Table 4.57 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos phase, nitric
acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[Volume %]
30
30
30
30

HNO3 with 30g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.800
1.610
2.420
3.300

Kd
(org./aq.)
[-]
0.250
0.242
0.240
0.212

Table 4.58 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[Volume %]
40
40
40
40

HNO3 with 30g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.755
1.516
2.290
3.100

K d (org./aq.)
[-]
0.324
0.319
0.310
0.290

Table 4.59 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP
[Volume %]
50
50
50
50

HNO3 with 30g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.720
1.449
2.180
2.950

K d (org./aq.)
[-]
0.388
0.380
0.376
0.355

Page | 81

Table 4.60 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP
[Volume %]
60
60
60
60

HNO3 with 30g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.680
1.390
2.100
2.820

K d (org./aq.)
[-]
0.471
0.438
0.428
0.418

Table 4.61 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

TBP
[Volume %]
70
70
70
70

HNO3 with 30g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.640
1.310
1.980
2.711

K d (org./aq.)
[-]
0.562
0.526
0.515
0.475

Table 4.62 Equilibrium concentration of nitric acid in presence of 30 g/l NaNO3 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

TBP
[Volume %]
80
80
80
80

HNO3 with 30g/l


NaNO3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.600
1.230
1.850
2.510

K d (org./aq.)
[-]
0.666
0.626
0.621
0.593

Fig. 4.23 shows the variation of nitric acid concentration in extract with that in raffinate for
different initial concentration of TBP (30 - 80%) in kerosene and in presence of 30 g/l
NaNO3, extraction experiments were carried out using O/A ratio of 1:1 at 25oC nitric acid
concentration in feed solution were in the range of 14 M. It was found that like in previous

Page | 82

cases as the concentration of TBP in kerosene increases the concentration of nitric acid in
extract increases.

HNO3 concentration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in presence of 30 g/l NaNO3

Fig. 4.23 The variation of nitric acid concentration in extract with that in raffinate for different
initial concentration of TBP (30 80 %) in kerosene and in presence of 30 g/l NaNO3, extraction
experiments were carried out by using O/A ratio of 1:1 at 25oC nitric acid concentration in feed
solution were in the range of 14 M.

Result of tenth set of experiment are shown in Fig. 4.24, which shows that nitric acid
concentration in extract phase increases with increase from 30 80 volume percentage in
the concentration of TBP in kerosene. Moreover, it was also observed that the percentage
extraction of nitric acid increases from17.50 37.25% (Kd = 0.2120.593) for initial nitric
acid concentration of the feed solution was 4 M and as the TBP concentration varied in a
single stage extraction.

Page | 83

HNO3 concentration in extract phase [mol/l]

1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.24 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 30 g/l NaNO3.

4.12 Nitric Acid Extraction in Presence of 30 g/l Ca(NO3)2 by TBP Diluted


with Kerosene
The experimental results for the extraction of nitric acid in presence of 30 g/l Calcium
nitrate were carried out with 30-80 volume % TBP in kerosene are shown in Tables 4.634.68. Initial concentration of nitric acid was varied from 1 to 4 M and each set of
experiments were repeated at least two times. The reproducibility of the results was within
1%. Equilibrium concentration of nitric acid in raffinate after extraction was determined
by titration like in the previous cases. Tables 4.63-4.68 show the average value of results
in both the phases.

Page | 84

Table 4.63 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

30

0.798

0.253

30

1.631

0.226

30

2.450

0.224

30

3.320

0.204

TBP
[Volume %]

[-]

Table 4.64 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

40

0.755

0.324

40

1.520

0.315

40

2.330

0.287

40

3.140

0.273

TBP
[Volume %]

[-]

Table 4.65 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

50

0.710

0.408

50

1.450

0.379

50

2.210

0.357

50

2.960

0.351

TBP
[Volume %]

[-]

Page | 85

Table 4.66 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

60

0.681

0.468

60

1.370

0.459

60

2.100

0.428

60

2.810

0.423

TBP
[Volume %]

[-]

Table 4.67 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

70

0.640

0.562

70

1.310

0.526

70

1.970

0.522

70

2.700

0.482

TBP
[Volume %]

[-]

Table 4.68 Equilibrium concentration of nitric acid in presence of 30 g/l Ca(NO3)2 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Ca(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

80

0.600

0.666

80

1.220

0.639

80

1.880

0.596

80

2.550

0.569

TBP
[Volume %]

[-]

Page | 86

HNO3 concentration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


In the presence of 30 g/l Ca(NO3)2

Fig. 4.25 The extraction of nitric acid in the range of (14M) by various concentration of tributyl phosphate/kerosene (30 - 80%) at an organic to aqueous phase ratio (O/A= 1), and at 25C
was determined in presence of 30 g/l Ca(NO3)2.

Fig. 4.25 shows that the change of the equilibrium concentration of nitric acid in organic
i.e., extract phase with that in raffinate phase for different initial concentrations of TBP in
kerosene. All the experiments were carried out by using O/A ratio of 1:1 and at room
temperature with one stage extraction process in presence of 30 g/l Ca(NO3)2 in feed
solution. It was found that the concentration of nitric acid in the extract increases with
increase in the initial concentration of TBP in kerosene increase from 30-80 volume % in
kerosene. The experimental results show that the presence of Ca(NO3)2 in feed solution
Page | 87

enhances the extraction of nitric acid compared to that in absence of Ca(NO3)2 in feed
solution.

HNO3 concentration in extract phase [mol/l]

1.6
1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2
1.0
0.8
0.6
0.4
0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig.4.26 Variation of nitric acid concentration in organic phase with the initial concentration of
TBP in kerosene in presence of 30 g/l Ca(NO3)2 in feed solution.

Fig. 4.26 shows the result of the eleventh set of experimental results, the variation of nitric
acid concentration in organic phase with the initial concentration of TBP in kerosene in
presence of 30 g/l Ca(NO3)2 in feed solution. It was observed that the percentage extraction
of nitric acid increases from17.00 36.25% (Kd= 0.2050.568) as the TBP concentration
increases from 30 80 volume percentage in a single stage extraction. The experimental
results show that the presence of Ca(NO3)2 in feed solution play an important role by

Page | 88

enhancing the extraction of nitric acid compared to that in absence of Ca(NO3)2 in feed
solutions.

4.13 Nitric Acid Extraction in Presence of 30 g/l Mg(NO3)2 by TBP Diluted


with Kerosene
The experimental results for the extraction of nitric acid in presence of 30 g/l magnesium
nitrate, carried out with 30-80 volume % TBP in kerosene are shown in Tables 4.69-4.74.
Initial concentration of nitric acid was varied from 1 to 4 M and each set of experiments
were repeated at least two times. The reproducibility of the results was within 1%.
Equilibrium concentration of nitric acid in raffinate after extraction was determined by
titration. Tables 4.69-4.74 show the average value of results in both the phases.

Table 4.69 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

Kd

HNO3 with 30 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

(org./aq.)

[M]

[M]

[-]

30

0.781

0.280

30

1.600

0.250

30

2.400

0.250

30

3.210

0.246

TBP
[ Volume %]

Page | 89

Table 4.70 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

40

0.740

0.351

40

1.510

0.324

40

2.280

0.315

40

3.060

0.307

TBP
[ Volume %]

[-]

Table 4.71 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

50

0.713

0.402

50

1.430

0.398

50

2.160

0.388

50

2.910

0.374

TBP
[ Volume %]

[-]

Table 4.72 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

Kd

HNO3 with 30 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

(org./aq.)

[M]

[M]

[-]

60

0.670

0.492

60

1.370

0.459

60

2.070

0.449

60

2.770

0.444

TBP
[ Volume %]

Page | 90

Table 4.73 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

70

0.632

0.582

70

1.300

0.538

70

1.970

0.522

70

2.690

0.486

TBP
[ Volume %]

[-]

Table 4.74 Equilibrium concentration of nitric acid in presence of 30 g/l Mg(NO3)2 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene).

HNO3 with 30 g/l

Concentration of

Mg(NO3)2

HNO3 in raffinate

[M]

[M]

K d (org./aq.)

80

0.600

0.666

80

1.220

0.639

80

1.840

0.630

80

2.500

0.600

TBP
[ Volume %]

[-]

Fig. 4.27 shows the variation of equilibrium concentration of nitric acid in extract with that
in raffinate for different initial concentrations of TBP in kerosene for single stage extraction
and phase ratio 1:1, 25oC and in presence of 30 g/l Mg(NO3)2 in feed solution. It was
observed that the percentage extraction of nitric acid increases from 17.00 36.25% (Kd=
0.2050.568) as the TBP concentration increases from 30 80 volume percentage in a
single stage extraction.

Page | 91

HNO3 concentration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in the presence of 30 g/l Mg(NO3)2
Fig. 4.27 The extraction of nitric acid in the range of (14 M) by various concentration of tributyl phosphate/kerosene (30 80 %) at an organic to aqueous phase ratio (O/A= 1), and at 25C
was determined in presence of 30 g/l Mg(NO3)2 in feed solution.

Fig. 4.28 shows the experimental results for twelfth set of experimental results; the variation
of equilibrium concentration of nitric acid in extract with that in raffinate for different initial
concentrations of nitric acid in feed solution for single stage extraction and phase ratio 1:1,
at 25oC and in presence of 30 g/l Mg(NO3)2 in feed solution. It was observed that the
percentage extraction of nitric acid increases as the nitric acid concentration increases in
feed solution.

Page | 92

HNO3 concentration in extract phase [mol/l]

1.4

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.2

1.0

0.8

0.6

0.4

0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.28 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 30 g/l Mg(NO3)2.

4.14 Nitric Acid Extraction in Presence of 30 g/l Al(NO3)3 by TBP Diluted


with Kerosene
The experiments for the extraction of nitric acid in presence of 30 g/l aluminium nitrate
were carried out with 30-80 volume % TBP in kerosene and experimental results are
shown in Tables 4.75-4.80. The initial concentration of nitric acid was varied from 1 to 4
M and each set of experiments were repeated at least two times. The reproducibility of the
Page | 93

results was within 1%. Equilibrium concentration of nitric acid in raffinate after
extraction was determined by titration as mentioned earlier. Tables 4.75-4.80 show the
average value of results in both the phases.

Table 4.75 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 30% TBP (diluted with kerosene).

TBP
[volume %]
30
30
30
30

HNO3 with 30 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.761
1.540
2.330
3.120

Kd
(org./aq.)
[-]
0.314
0.298
0.287
0.282

Table 4.76 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 40% TBP (diluted with kerosene).

TBP
[volume %]
40
40
40
40

HNO3 with 30 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.732
1.470
2.220
3.000

K d (org./aq.)
[-]
0.366
0.360
0.351
0.333

Table 4.77 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 50% TBP (diluted with kerosene).

TBP
[volume %]
50
50
50
50

HNO3 with 30
g/l Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.700
1.405
2.120
2.850

K d (org./aq.)
[-]
0.428
0.423
0.415
0.403

Page | 94

Table 4.78 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 60% TBP (diluted with kerosene).

TBP
[volume %]
60
60
60
60

HNO3 with 30 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.653
1.338
2.030
2.710

K d (org./aq.)
[-]
0.531
0.494
0.477
0.476

Table 4.79 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 70% TBP (diluted with kerosene).

TBP
[volume %]
70
70
70
70

HNO3 with 30 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.621
1.260
1.920
2.630

K d (org./aq.)
[-]
0.610
0.587
0.562
0.520

Table 4.80 Equilibrium concentration of nitric acid in presence of 30 g/l Al(NO3)3 in aqueos phase,
nitric acid was extracted by using 80% TBP (diluted with kerosene)..

TBP
[volume %]
80
80
80
80

HNO3 with 30 g/l


Al(NO3)3
[M]
1
2
3
4

Concentration of
HNO3 in raffinate
[M]
0.580
1.165
1.800
2.440

Kd
(org./aq.)
[-]
0.724
0.716
0.666
0.639

Fig. 4.29 shows the variation of equilibrium concentration of nitric in extract with that in
raffinate for different initial concentration of TBP in kerosene and initial nitric acid
concentration in feed 4M and in presence of 30 g/l Al(NO3)3. Organic to aqueous phase ratio,
O/A= 1 and experiments were carried out at 25C. It was found that as the initial concentration

Page | 95

of TBP in kerosene increases, the equilibrium concentration of nitric acid in extract increases
in presence of Al(NO3)3 in feed solution.

HNO3 concentration in extract phase [mol/l]

1.6
30 % TBP
40 % TBP
50 % TBP
60 % TBP
70 % TBP
80 % TBP

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.5

1.0

1.5

2.0

2.5

3.0

3.5

HNO3 concentration in raffinate phase [mol/l]


in presence of 30 g/l Al(NO3)3

Fig. 4.29 Variation of equilibrium concentration of nitric in extract with that in raffinate for
different initial concentration of TBP in kerosene and initial nitric acid concentration in feed 4
M and in presence of 30 g/l Al(NO3)3. Organic to aqueous phase ratio, O/A= 1 and experiments
were carried out at 25C.

Fig. 4.30 shows the variation of nitric in organic phase with TBP concentration in kerosene.
The initial nitric acid concentration in feed was varied from 1-4M in presence of 30 g/l
Al(NO3)3. Organic to aqueous phase ratio, O/A = 1 and experiments were carried out at 25C.
It was found that as the initial concentration of nitric acid in feed solution increases, the
equilibrium concentration of nitric acid in extract increases in presence of Al(NO3)3 in feed
solution. It was also observed that the percentage extraction of nitric acid increases from
22.00 39.00% (Kd= 0.2820.639) as the nitric acid concentration varied from 1-4 M in a
single stage extraction.
Page | 96

HNO3 concentration in extract phase [mol/l]

1.6

1M Nitric acid
2M Nitric acid
3M Nitric acid
4M Nitric acid

1.4
1.2
1.0
0.8
0.6
0.4
0.2
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.30 Variation of nitric acid concentration in organic phase with TBP concentration in
presence of 30 g/l Al(NO3)3.

Experimental results for the percentage extraction with the concentration of TBP (in volume
%) are presented here for individual inextractable metal nitrates which gives four lines
correspondingly without nitrates, 10 g/l, 20 g/l and 30 g/l concentration of different metal
nitrates.
It was observed that percentage extraction enhance slowly as the NaNO3 concentration
increases as shown in Fig. 4.31. In presence of Mg(NO3)2 of different concentration
percentage extraction increases faster than NaNO3 as shown in Fig. 4.32. On the other hand as
the concentration of Al(NO3)3 increases in the aqueous phase; the percentage extraction of
nitric acid increases drastically as shown in Fig. 4.33 and the same for the presence of
Ca(NO3)2 are similar compared to that of NaNO3 as show in Fig. 4.34.

Page | 97

Percentage extraction [E, %]

40

without nitrates
with 10 g/l NaNO3
with 20 g/l NaNO3
with 30 g/l NaNO3

35

30

25

20

15
30

40

50

60

70

80

Concentration of TBP in kerosene [ volume %]

Fig. 4.31 Effect of the presence of NaNO3 concentration on of the extraction nitric acid of initial
concentration 2 M by using TBP diluted with kerosene.

Percentage extraction [E, %]

40
without nitrates
with 10 g/l Mg(NO3)2
with 20 g/l Mg(NO3)2
with 30 g/l Mg(NO3)2

35

30

25

20

15
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.32 Effect of the presence of Mg(NO3)2 of different concentration in feed solution on of the
extraction nitric acid of initial concentration 2 M in feed solution by using TBP diluted with
kerosene.

Page | 98

45

Percentage extraction [E, %]

40

without nitrates
with 10 g/l Al(NO3)3
with 20 g/l Al(NO3)3
with 30 g/l Al(NO3)3

35

30

25

20

15
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.33 Effect of the presence of Al(NO3)3 of different concentrations on the extraction nitric
acid of initial concentration 2 M in feed solution by using TBP diluted with kerosene.

Percentage extraction [E, %]

40

without nitrates
with 10 g/l Ca(NO3)2
with 20 g/l Ca(NO3)2
with 30 g/l Ca(NO3)2

35

30

25

20

15
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.34 Effect of the presence of Ca(NO3)2 of different concentrations on the extraction nitric
acid of initial concentration 2 M in feed solution by using TBP diluted with kerosene.

Page | 99

4.15 Effect of TBP Concentration on the Extraction of Nitric Acid


The extraction mechanism of nitric acid by TBP can be expressed by the Reaction (15).

H++ NO3+ TBP

TBP.HNO3

(15)

The equilibrium constant of Reaction (15) can be written as shown in Eq. (16).

. 3

+ . 3 .

KHNO3 =

(16)

Taking the logarithm of both sides of Eq. (16) and rearranging, we obtain Eq. (17).

log

.3

= logKeq + logTBP ,

where, .3 = 3

The log-log plots of CHNO 3

org

/(CH+ . CNO3 )

(17)

versus TBP produced four straight lines

representing for initial nitric acid concentrations of 1 M, 2 M, 3 M, 4 M with a slope of 0.811,


0.917, 1.023 and 1.124 respectively and regression coefficients of 0.988, 0.994, 0.996 and
0.997, respectively as shown in Fig. 4.35. These results suggest a linear relationship between
extraction of HNO3 with TBP concentration and one molecule of HNO3 is extracted by one
molecule of TBP. Moreover the slope of the lines increases with the increase in concentration
of nitric acid in the feed solution. The experimental results are presented in Table 4.81.

Page | 100

Table 4.81 Experimental data of log-log plots of CHNO 3

org

/(CH+ . CNO3 ) versus TBP in the

absence of metal nitrate.

log CTBP

CHNO 3

log C

org

H+ .CNO3

CHNO 3

log C

org

H+ .CNO3

CHNO 3

log C

org

H+ .CNO3

CHNO 3

log C

H+

org

.CNO3

[M]

1M

2M

3M

4M

0.040

-0.630

-0.673

-0.720

-0.771

0.1655

-0.501

-0.550

-0.611

-0.650

0.262

-0.454

-0.477

-0.517

-0.537

0.341

-0.389

-0.399

-0.421

-0.429

0.408

-0.327

-0.347

-0.354

-0.364

0.466

-0.269

-0.269

-0.288

-0.301

It was found that in presence of 20 g/l NaNO3 the log-log plots of CHNO 3

org

/(CH+ . CNO3 )

versus TBP produced four straight lines for the initial nitric acid in feed solution of 1M, 2 M, 3

M, 4 M, with a slope of 0.961, 0.963, 0.995 and 1.014 and regression coefficients of 0.993,
0.994, 0.993 and 0.997 respectively.
In the presence of 20 g/l Mg(NO3)2in feed solution the log-log plots of CHNO 3

org

(CH+ . CNO3 ) versus TBP gives four straight line for the initial nitric acid concentration of 1

M, 2 M, 3 M, 4 M with a slope of 0.887, 0.942, 0.961 and 0.945 and regression coefficients of
0.985, 0.991, 0.993 and 0.997 respectively.

Page | 101

-0.2

1M [HNO3]i
2M [HNO3]i
3M [HNO3]i
4M [HNO3]i

-0.3

log CHNO , /CH C

NO3

-0.4

3 org

-0.5

-0.6

-0.7

-0.8
0.0

0.1

0.2

0.3

0.4

0.5

log CTBP
Fig. 4.35 Effect of the concentration of TBP in kerosene on the extraction of nitric acid of initial
concentration of nitric acid in feed solution 1-4 M, in the absence of metal nitrate ions.

In the presence of 20 g/l Al(NO3)3 the log-log plots of CHNO 3

org

/(CH+ . CNO3 ) versus TBP

gave four straight lines of corresponding 1 M, 2 M, 3 M, 4 M, initial nitric acid with a slope of
0.845, 0.841, 0.844 and 0.814 and regression coefficients of 0.963, 0.971, 0.977 and 0.989.

4.16 Stripping of Nitric Acid from Extract


Demineralised water was used as the stripping agent. The results showed that stripping
efficiency varied with the concentration of TBP in extract phase (loaded organic). And the
percentage recovery of nitric acid decreases with increase in the concentration of TBP.
Stripping of nitric acid from loaded organic was carried out by using O/A ratio 1:1 in a
separating funnel and it was found that the percentage recovery of nitric acid varies from

Page | 102

75.6% to 69.45% as the TBP concentration changes from 30-80 volume % as shown in Fig.
4.36. The percentage recovery of nitric acid is defined in this thesis as follows.

Percentage recovery =

nitric acid concentration in extract phase


X100
initial nitric acid concentration in organic phase

Fig. 4.36 represents the experimental results for the stripping of nitric acid from extract by
using DM water with O/A ratio of 1:1. A constant mixing time of 2 min was used in each
experiment. The average value of the percentage recovery of nitric acid for four set of
experiments for the initial nitric acid concentrations in aqueous solution of 1-4 M and
extraction with TBP solution was considered.

% Recovery in stripping with DM water [%]

76
75
74
73
72
71
70
69
30

40

50

60

70

80

Concentration of TBP in kerosene [volume %]

Fig. 4.36 Stripping of nitric acid from extract by using DM water with O/A ratio of 1:1 at
constant mixing time of 2 min. The average value of the % recovery of four set of experiments
for the initial nitric acid concentrations in aqueous solution of 1-4 M and extraction with TBP
solution was considered.

Page | 103

Chapter 5

Conclusions and future work

5.1 Conclusions
From the experimental results it was observed that nitric acid can be extracted from effluent
containing free nitric acid by using dilute TBP (in kerosene) solution of O/A ratio 1:1. The
presence of different metal nitrates viz., Na+, Mg+2, Ca+2, Al+3 etc. of different
concentrations enhances the degree of recovery of nitric acid from aqueous nitric acid
solution. It was also found that the percentage extraction of nitric acid in presence of
Al(NO3)3 was higher than that of other metal nitrates and the same also increases with
increase in concentration of TBP in kerosene.

The cation associated with the nitrate impacts the effectiveness of the salting-out agent. The
distribution coefficient increases as the ionic radius of the metal cation of the salting agent
decreases. For example, the effectiveness of the salting-out agent decreases as, Al(NO3)3 >
Mg(NO3)2 > NaNO3 ~ Ca(NO3)2. The smaller cation essentially provides free nitrate in
solution since the dissociation of the ions is greater. It was found that the slope of the
straight line of log-log plots of CHNO 3

org

/(CH+ . CNO3 ) versus TBP decreases as the ionic

radius of the metal cation of the salting agent decreases. However, the percentage extraction
of nitric acid increases as the ionic radius of the metal cation of the salting agent decreases.
It indicates that the amount of free TBP decreases as the radius of metal cation decreases
Page | 104

and the more amount of TBP is forming complex with HNO3 and nitric acid extraction is
increases (as found from the experimental result, that Kd value increases) as the radius of
metal cation decreases.

The percentage extraction of nitric acid can be increased by using higher concentration of
TBP, as the concentration of TBP increases percentage extraction of nitric acid increases.
The extracted nitric acid may be stripped by using DM water with O/A ratio of 1:1. It was
found that 69 to 76% of nitric acid can be recovered in a single stages extraction. The
percentage recovery of nitric acid is decreasing by using higher concentration of TBP in
stripping, as the concentration of TBP increases the percentage recovery decreases which
can be enhance by increasing the O/A ratio and mixing time. However, by using multistage
extraction the complete extraction of nitric acid is possible.

Experiments were carried out to recover nitric acid from acidic raffinate solution by
extraction with TBP-diluent system. The effect of different parameters was studied and the
possible mechanism for the effect was postulated. The parameters which affect the
extraction of nitric acid are listed below.

1.

Initial concentration of nitric acid in feed solution,

2.

Initial concentration of TBP in kerosene,

3.

Nitrate ion concentrations in feed solution and

4.

Size of cations present in the feed solution.

Page | 105

By recovering nitric acid from effluent containing free nitric acid the total nitrate
concentration in the effluent can be reduced, which in turn can solve the disposal of nitrate
bearing effluents. Moreover, the recovered nitric acid can be reused, which in turn can
reduce the processing cost. Further work is required for the optimization of various process
parameters.

5.2 Future Work


The following works are proposed which may be carried out in future.
1.

Molecular modelling to find better solvents for the extraction of nitric acid from
aqueous solution containing free nitric acid.

In this study TBP was used as a solvent for nitric acid extraction from acidic solution
containing metal nitrates and it was mentioned that there is a mutual solubility of both the
phases, which leads the losses of TBP and reduce the extractability. Moreover, TBP has
some drawbacks viz.; it is soluble in water and degrades over a period of time. It is
suggested to find out better solvent which can recover nitric acid with higher Kd value for
a given initial concentration of nitric acid in aqueous phase and which does not has these
drawbacks.
2. Optimization of process parameters.

A process parameter like O/A ratio in extraction, stripping and number of stages may be
optimized in addition to find better extraction equipments which can give better
recoverability for the plant scale operation.

Page | 106

3. Study on the Effect of Mixture of Nitrates in Feed Solution

Study on the effect of mixture of different metal nitrates; commonly present in effluent
containing free nitric acid on the extraction of nitric acid which was not covered in the
present study.

Page | 107

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************

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