Analysis of Urea Electrolysis for Generation of Hydrogen

A thesis presented to

the faculty of

the Russ College of Engineering and Technology of Ohio University

In partial fulfillment

of the requirements for the degree

Master of Science

Deepika Singh

November 2009
 2

This thesis titled

Analysis of Urea Electrolysis for Generation of Hydrogen

by

DEEPIKA SINGH

has been approved for

the Department of Chemical and Biomolecular Engineering

and the Russ College of Engineering and Technology by

Gerardine G. Botte

Associate Professor of Chemical and Biomolecular Engineering

Dennis Irwin

Dean, Russ College of Engineering and Technology

 3

ABSTRACT

SINGH, DEEPIKA, M.S., November 2009, Chemical Engineering

Analysis of Urea Electrolysis for Generation of Hydrogen (100 pp.)

Director of Thesis: Gerardine G. Botte

The oxidation of urea was studied as a means of remediating urine-rich waste

water to produce hydrogen and simultaneously denitrificating the waste water. The

proposed reaction mechanisms, preferred pathway and rate determining steps have been

predicted using Density Functional Theory calculations. Both the electro-oxidation

reaction as well as the chemical oxidation reaction mechanisms have been postulated on

the surface of the active catalyst NiOOH. The preferred pathway for electro-oxidation

was found to be: *CO(NH2)2→ *CO(NH.NH2)→ *CO(NH.NH)→

*CO(NH.N)→*CO(N2) → *CO(OH) →*CO(OH.OH) →*CO2 with desorption of CO2

as the rate limiting step. From the thermodynamic calculations of the chemical oxidation

reactions, it was evident that the presence of OH- catalyzes the reaction. Experimentally,

the effects of varying concentrations of KOH and urea were investigated. The

experimental results supported the argument that a higher concentration of OH- is more

favorable for the reaction.

Approved: _____________________________________________________________

Gerardine G. Botte

Associate Professor of Chemical and Biomolecular Engineering

 4

ACKNOWLEDGMENTS

Firstly I would like to acknowledge the guidance, motivation and tremendous

support of my advisor, Dr. Gerardine Botte. She will continue to be a source of

inspiration for me throughout my career. I would also like to thank my colleagues at the

Electrochemical Engineering Research Laboratory for their guidance and patience in

helping me learn the basic laboratory techniques. In particular, I want to acknowledge the

tremendous contribution of Damilola Daramola who has helped me from the initial stages

of teaching computational techniques right untill the end for editing and formatting of the

submitted publications, apart from mentoring me at all stages in my research. Without his

support none of this would have possible. I would also like to extend my heartiest

gratitude to the Ohio Super Computing Center for providing valuable resources and

computing time for the computational calculations.

I would also like to thank all friends, especially Saurin Shah and Santosh Vijapur

for being there for me all the time. For all the emotional and moral support and for

believing in me, for giving me the strength to persevere, I can never thank both of you

enough. Finally I’d like to thank my immediate family who has always been there with

me mentally, if not physically. For their undying belief, the kind words and unfailing

support. For being with me through thick and thin, at all times of the day. Thank you so

much. I could not have done this without you all.

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TABLE OF CONTENTS

Page

Abstract ............................................................................................................................... 3 

Acknowledgments............................................................................................................... 4 

List of Tables ...................................................................................................................... 7 

List of Figures ..................................................................................................................... 8 

Chapter 1 : Introduction .................................................................................................... 10 

1.1  Project Overview .............................................................................................. 10 

1.2  Statement of Objectives .................................................................................... 13 

1.3  Significance of Research................................................................................... 14 

Chapter 2 : Literature Review ........................................................................................... 15 

2.1  Theoretical ........................................................................................................ 15 

2.2  Experimental ..................................................................................................... 18 

Chapter 3 : Computational Methods ................................................................................. 19 

Chapter 4 : Electro-Oxidation Mechanisms ...................................................................... 23 

4.1  Reaction Mechanism Path 1.............................................................................. 25 

4.2  Reaction Mechanism: Path 2 ............................................................................ 36 

4.3  Reaction Mechanisms: Path 3 ........................................................................... 41 

4.5  Conclusion ........................................................................................................ 49 

Chapter 5 : Chemical Oxidation Mechanisms .................................................................. 51 

5.1  Different Orientations of Urea towards NiOOH ............................................... 51 

5.2  Urea decomposition with NiOOH ................................................................... 53 

5.3  Urea and NiOOH in the presence of OH- ion: .................................................. 55 

5.4  Conclusion ........................................................................................................ 58 

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Chapter 6 : Experimental .................................................................................................. 59 

6.1  Experimental Methods: Electroplating and Preliminary Results ...................... 59 

6.2  Potentio-dynamic Tests ..................................................................................... 60 

6.3  Results and Discussion ..................................................................................... 61 

6.4  Conclusion ........................................................................................................ 64 

Chapter 7 : Conclusions and Recommendations .............................................................. 65 

References ......................................................................................................................... 67 

Appendix A: Supporting Information for Urea Electro-Oxidation Reaction ....................72

Appendix B: Supporting Information for Urea Chemical Oxidation Reaction .................93

 7

LIST OF TABLES

Page

Table 3.1: Bond lengths and bond angles of urea as computed using different basis sets
with the B3LYP correlational functional ...........................................................................20

Table 3.2 : Experimental bond lengths for NiOOH kept constant for the reaction
mechanisms ........................................................................................................................20

Table 4.1: Proposed reaction mechanisms for urea electro oxidation reaction .................25

Table 4.2: Sum of free energies for all the intermediate steps...........................................48

Table 4.3: Kinetics of the reaction pathways and rate constants for intermediate steps ...49

Table 5.1: Binding Energies of different orientations of urea towards NiOOH ................53

Table 5.2: Free Energies differences for Equations 5.1 and 5.2 ........................................55

Table 5.3: Free Energies differences for Equations 5.3 and 5.4 ........................................58
 8

LIST OF FIGURES

Page

Figure 1.1:Global Energy Systems Transition1 ................................................................ 10 

Figure 2.1: Mechanism of urease catalyzed urea hydrolysis14 ......................................... 16 

Figure 4.1: Initial state (a) Transition state (b) and Final structure (c) for
Equation 4.5 ...................................................................................................................... 26 

Figure 4.2: Initial state (a), transition state (b) and final structure (c) for
Equation 4.6 ...................................................................................................................... 27 

Figure 4.3: Initial state (a), transition state (b) and final structure (c) for
Equation 4.7 ...................................................................................................................... 29 

Figure 4.4: Initial state (a), transition state (b) and final structure (c) for
Equation 4.8 ...................................................................................................................... 30 

Figure 4.5: Initial state (a), transition state (b) and final structure (c) for
Equation 4.9 ...................................................................................................................... 31 

Figure 4.6: Initial state (a), transition state (b) and final structure (c) for re-arrangement
of nitrogen atoms .............................................................................................................. 32 

Figure 4.7: Initial state (a), transition state (b) and final structure (c) for Equation 4.10..
.......................................................................................................................................... .34 

Figure 4.8: Initial state (a), transition state (b) and final structure (c) for
Equation 4.11 .................................................................................................................... 35 

Figure 4.9: Initial state (a), transition state (b) and final structure (c) for
Equation 4.12 .................................................................................................................... 36 

Figure 4.10: Initial state (a), transition state (b) and final structure (c) for
Equation 4.13 .................................................................................................................... 37 

Figure 4.11: Initial state (a), transition state (b) and final structure (c) for
Equation 4.14 .................................................................................................................... 38 
 9

Figure 4.12: Initial state (a), transition state (b) and final structure (c) for
Equation 4.15 .................................................................................................................... 39 

Figure 4.13: Initial state (a), transition state (b) and final structure (c) for
Equation 4.16 .................................................................................................................... 40 

Figure 4.14: Initial state (a), transition state (b) and final structure (c) for rearrangement
of amine groups................................................................................................................. 42 

Figure 4.15: Initial state (a), transition state (b) and final structure (c) for Equation
4.17……………………………………………………………………………………….42 

Figure 4.16: Initial state (a), transition state (b) and final structure (c) for
Equation 4.18 .................................................................................................................... 44 

Figure 4.17: Initial state (a), transition state (b) and final structure (c) for Equation 4.17.
........................................................................................................................................... 45 

Figure 5.1: Optimized structures for different orientations of urea towards NiOOH ....... 52 

Figure 5.2: Optimized structures for Equations 5.1 and 5.2 ............................................. 54 

Figure 5.3: Optimized Transition States for Reactions 2 and 3 ........................................ 55 

Figure 5.4: Adsorption of OH- onto NiOOH .................................................................... 56 

Figure 5.5: Optimized structures for Equations 5.3 and 5.4. ............................................ 56 

Figure 5.6: Transition State Structures for Equations 5.3 and 5.4 .................................... 57 

Figure 6.1: Preliminary experiment. Different concentrations of KOH at 20g L-1 urea to
determine lower setpoint. .................................................................................................. 62 

Figure 6.2: Urea concentration of 5 g L-1 varying KOH concentrations. Scan rate:
20mV s-1. Speed of rotation: 1000rpm.............................................................................. 63 

Figure 6.3: Urea Concentration of 10 g L-1 with varying KOH concentrations. Scan Rate:
20mV s-1. Speed of rotation 1000rpm. .............................................................................. 63 

Figure 6.4: Urea concentration of 20 g L-1 with varying KOH concentrations. Scan rate
20mV s-1. Speed of rotation 1000 rpm. ............................................................................. 64 
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Chapter 1 : INTRODUCTION

1.1 Project Overview

The use of hydrogen as an alternative fuel has been the focus of attention for many

decades now, especially as the demand for fuels from renewable energy sources is

constantly on the rise. The transition from liquid petroleum to gases over a span of 200

years is as shown in Figure 1.1. According to this trend, there will be a complete shift

from petroleum to hydrogen for meeting world energy requirements by the turn of the

next century1.

Figure 1.1:Global Energy Systems Transition1

 11

The devices that produce hydrogen for the purpose of electricity generation are

called fuel cells. They operate on the principle of recombination of hydrogen with oxygen

to release energy and produce water as a byproduct. Although there are five different

types of fuel cells being developed for commercial applications, proton exchange

membrane fuel cells are considered as viable, low temperature operating devices for both

transportation and stationary applications2, 3.

Proton exchange membrane (PEM) fuel cells working on water electrolysis are

based on the mechanism of splitting up of the water molecule into hydrogen and oxygen

with the liberation of energy in an exothermic reaction. The water electrolysis reaction is

as follows:

Anode: H2 → 2H+ + 2e- (1.1)

Cathode: 4H+ + 4e- + O2→ 2H2O (1.2)

Heat Output T∆S= 48.7 kJ mol-1 4

The Electrochemical Engineering Research Laboratory (EERL) at Ohio

University has recently devised a new alternative to the water electrolysis reaction:

ammonia electrolysis in which the ammonia molecule dissociates to give nitrogen as

follows:

Anode: 2NH3 + 6OH-→ N2 + 6H2O + 6e- (1.3)

Cathode: 2H2O + 2e- → H2 + 2OH- (1.4)

 12

This process produces hydrogen to power PEM fuel cells and is a self sustainable

source of energy. It eliminates the problems associated with storing hydrogen as it

produces hydrogen on demand5-7.

An alternative to the above mentioned ammonia electrolysis process is urea

electrolysis, by means of which urine from animal farms and waste water lagoons can be

directly utilized to produce hydrogen to power fuel cells8. Urea is known to naturally

decompose to ammonia, hence is a major issue among farmers regarding taxes on

ammonia emissions9. This process once commercialized will not only help farmers

receive tax cuts for reduced ammonia emissions, but it will also decrease their

dependence on fossil fuels for power generation.

Urea electrolysis in alkaline medium is being investigated at the Electrochemical

Engineering Research Laboratory (EERL) at Ohio University as a novel technique for

hydrogen production. This project is of importance as it addresses the need to remediate

waste water from poultry farms as well as residential and commercial areas and using it

as a tool to solve one of the world’s impending energy crises. This following project was

undertaken to understand urea electrolysis for the purpose of generation of hydrogen for

fuel cells using theoretical and experimental methods.

Experimental methods will be combined with molecular modeling to gain a better

understanding of the electrolysis process. The reaction mechanisms are being studied

both chemically and electrochemically using the Gaussian 03 software. Experimental

techniques involve studying the effect of reaction parameters using a rotating disk

electrode.
 13

1.2 Statement of Objectives

The purpose of this thesis is to gain a better understanding of the urea electrolysis

process in order to aid further development of the technology to make it commercially

viable for fuel cells. The following objectives are proposed to be accomplished with the

completion of the thesis.

1) Postulating reaction mechanisms for urea electrolysis using molecular modeling

techniques along with activation energies and rate constant calculations both in terms

of chemical oxidation and electrochemical oxidation. Under this objective, two

possible scenarios were considered:

i) Chemical Decomposition: Urea is known to dissociate naturally to ammonia

and carbamates. This reaction has been studied in the presence of the catalyst

nickel oxyhydroxide.

ii) Electrochemical Oxidation: Urea has also been found to undergo

electrochemical oxidation as found by the Electrochemical Engineering

Research Laboratory according to the following reactions:

Anode: CO(NH2)2(aq) + 6OH-→ N2(g) + 5H2O(l) + CO2 (aq) + 6e- (1.5)

Cathode: 6H2O (l) + 6e-→ 3H2(g) + 6OH- (1.6)

Overall: CO(NH2)2(aq) + H2O(l) → N2(g) + 3H2(g) + CO2 (aq) (1.7)

The elementary steps involved in the anodic reaction have been studied.

2) Determining the effect of reaction parameters such as concentration of potassium

hydroxide (KOH) and urea on process.

 14

With the help of these reaction mechanisms and by determining the preferred

pathway as well as the rate determining step, measures can be taken to improve

efficiency of the process experimentally.

1.3 Significance of Research

The most important technological impact of this project arises from the utilization

of the most abundant waste on earth, urine, to produce cheap electricity. Apart from

being a significant source of hydrogen production, this technology can also be used to de-

nitrificate waste water, thus saving a huge amount of expenditure on waste water

remediation. At present, the permissible nitrate concentration in water is 10 mg L-1

however, most denitrification processes are expensive and ineffective10. Natural

hydrolysis of urea to ammonia leads to the formation of ammonium sulfate and

ammonium nitrate in the atmosphere which pose significant health hazards11. Hence, by

electrolyzing urea to useful products, we are able to bypass the formation of the hazard-

causing products.

Another important aspect is that the electrolytic cell potential required for the

overall reaction to occur is only 0.37 V at standard conditions. When this is compared to

the cell potential required to produce hydrogen (1.23 V), it amounts to generation of 70%

cheaper hydrogen theoretically12.

These factors emphasize the need for a better understanding of the ongoing

process, which has been achieved in this project by means of the invaluable tool of

molecular modeling.
 15

Chapter 2 : LITERATURE REVIEW

2.1 Theoretical

Urea electrolysis is a modification of the ammonia electrolysis technology for the

purpose of generating hydrogen for fuel cells. Urea hydrolysis and decomposition

mechanisms have generated interest in the past in varied fields including removal of urea

from the blood using dialyzers and also formulation of urease inhibitors for better soil

fertility. When urea dissociates in the presence of the bio enzyme urea amidohydrolase 13-
15
(urease), it leads to a sudden increase in pH of the soil due to the liberation of ammonia,

leading to its decreased fertility thus rendering it ineffective for agricultural purposes16, 17.

For this reason, biocatalytic decomposition of urea by urease which catalyzes the

reaction has been given considerable attention in the literature18-20. Urease decomposes

urea to ammonia and carbon dioxide under specific reaction conditions according to the

following reactions21:

CO(NH 2 )2 ⎯⎯ ⎯→ NH 3 + HNCO
urease
(2.1)

NH3 + HNCO +H2O → 2NH3 + CO2 (2.2)

The enzyme urease comprises of two pseudo-octahedral Ni(II) ions as its active

sites. Suarez et al.13 have proposed the reaction mechanisms for urea hydrolysis.

According to their work, urea binds to the two active nickel sites in urea in a bidentate

manner. The more electrophilic nickel attaches itself to the carbonyl group of urea, while

the other nickel atom attacks one of the amino groups. They have considered a bridging

hydroxide group between the two nickel atoms, which donates a proton to the amino

group that is attached to the second nickel atom as shown in Figure 2.1.
 16

Figure 2.1: Mechanism of urease catalyzed urea hydrolysis13

The mechanism of urea decomposition in aqueous phase has been further studied

by different authors 15, 22, 23. This study was performed with the presence of urea in water

alone without the urease enzyme. In the aqueous solution, the elimination mechanism

yields isocyanic acid and ammonia, whereas intramolecular proton transfer gives cyanic

acid and ammonia18. It was also concluded that elimination mechanism greatly disrupts

the resonance stabilization of urea. However, Alexandrova and Jorgenson 18 have

analyzed the activation energies of elimination and hydrolytic mechanism pathways of

urea in aqueous solution and conclude that urea prefers to eliminate ammonia rather than

undergo hydrolysis.

These mechanisms are relevant in the context of this study because at EERL at

Ohio University, studies are being conducted for the electrolytic dissociation of urea for

the purpose of generating hydrogen for proton exchange membrane fuel cells24. Nickel

has been identified as the active catalyst for the reaction, which is supported by the fact
 17

that urea undergoes natural hydrolysis in the presence of the urease enzyme which has

nickel as its active site.

An alkaline medium is used to carry out the electrolysis, and nickel undergoes

oxidation to its active state: nickel oxyhydroxide (NiOOH) in this medium by the

following reaction:

Ni(OH)2(s) + OH- → NiOOH(s) + H2O (l) + e- (2.3)

Nickel oxyhydroxide plays the role of an active catalyst in many alkaline

batteries, and has thus received considerable attention in electrochemical research.

This reaction is hypothesized to occur on the surface of the nickel electrode in the

presence of urea as well. As a result, it is important to study the interaction of the nickel

oxyhydroxide molecule with urea to come up with feasible reaction mechanisms for the

nature of interactions on the electrode surface.

The above mentioned modeling calculations have been performed using Gaussian

03 softwares. In an analogy to experimental operating conditions, theoretical calculations

comprise of basis sets which are the pre-defined parameters within the confines of which

the calculations are performed.

In the past, quantum chemical calculations have been performed using Linear

Combination of Atomic Orbitals Molecular Orbitals (LCAO MO). These molecular

orbitals exist as a linear combination of atomic orbitals as follows:

௡

߰௜ ൌ ෍ ܿఓ௜ ߶ఓ
ఓୀଵ
 18

Where ψi is the ith molecular orbital, cμi are the coefficients of linear combination

andΦμis the μth atomic orbital and n is the number of atomic orbitals.25 These atomic

orbitals (AO) are solutions of the wave functions for a single electron in an atom. A basis

set is a set of these wave functions within the framework of which quantum chemical

calculations are performed. Basis sets play a crucial role in the binding energies obtained

from the molecular modeling calculations.

2.2 Experimental

Experimentally, urea electrolysis has been traditionally applied in techniques such

as dialysis and synthesis of carbon nitride thin films. These applications have been

studied in acidic medium with noble metals like platinum, iridium, ruthenium. Simka et

al.26 have investigated different compositions of Ti/(Pt-Ir), Ti/RuO2, Ti/(Ta2O5-IrO2) to

produce non toxic products with this reaction. But it is for the first time that alkaline

electrolysis of urea is being considered for the purpose of hydrogen production. Here we

have considered nickel as the catalyst for this reaction as it is cheap, economically

feasible and shows high activity for urea electrolysis. Currently, high concentrations of

alkali potassium hydroxide (KOH) are being used in the reaction. Typical concentration

used is 5 M (280 g L-1). It is important to examine the effect of KOH concentration to

investigate if lower concentrations can be used under the given operating conditions.
 19

Chapter 3 : COMPUTATIONAL METHODS

With the primary purpose of elucidating the reaction mechanism, single molecule

interactions of NiOOH with urea have been considered. DFT calculations were carried

out using the Gaussian 03 program27 with the B3LYP correlation functional28. A mixed

basis set was used comprising of Los Alamos National Laboratory of double zeta quality

(LANL2DZ)29-31 and 6-31g*32 for carbon, nitrogen hydrogen and oxygen atoms, also

referred to as the LACVP* basis set. The comparison of the relevant geometrical

features of the urea molecule was reported on the B3LYP level in literature33 (Table 3.1).

These values of bond angles and bond lengths reported using the 6-31g* basis set were

found to be reasonably accurate in comparison with the experimental values. Considering

its requirement of less processing time, 6-31g* was chosen as a building block for these

calculations.
 20

Table 3.1: Bond lengths and bond angles of urea as computed using different basis sets

with the B3LYP correlational functional.

Intra molecular bond lengths and angles (in Å and degree)

6-31g(d,p) DZP 6-311g(d,p) TZP exp

C-O 1.271 1.273 1.263 1.260 1.262

C-N 1.349 1.352 1.349 1.349 1.345

N-H1 1.014 1.022 1.012 1.011 1.009

O-C-N 121.4 121.4 121.6 121.6 121.4

N-C-N 117.1 117.2 116.9 116.7 117.2

C-N-H 119.9 119.9 119.9 120.0 119.1

For the electro oxidation reaction mechanisms the bond lengths for atoms of

NiOOH were kept constant at their experimental values34, 35 for the electrochemical

oxidation reactions as follows in Table 3.2:

Table 3.2 : Experimental bond lengths for NiOOH kept constant for the reaction

mechanisms

X-Y Pair Bond Length (Å)

Ni-O 1.88

Ni-OH 1.91

O-H 0.956
 21

No further geometry constraints were placed on the system. The Gaussian 03

algorithm was used to calculate the vibrational frequency and analytical force constant

calculations on all structures. The transition states for all elementary steps were located

implementing the default Gaussian 03 method. The transition state geometry possessed

two imaginary frequencies: one corresponding to the geometry constraint placed on

NiOOH (the O-H bond) and the other corresponding to the transition state (TS) structure.

Animation of the particular transition state negative frequency verified that the TS

corresponded to the interacting atoms for the particular step under consideration.

The rate constant calculations based on the transition state theory36 were performed using

partition functions as shown in the following equation:

⎛ ⎞
k BT ⎜ q # ⎟ ⎛ −E i ⎞
k= exp⎜ ⎟ (3.1)
h ⎜⎜ ∏n q ⎟⎟ ⎝ RT ⎠
⎝ j=1 j ⎠

where,

k= rate constant (L mol-1 s-1)

qt=partition function for transition state (Hartrees)

qr=partition function for reactant (Hartrees)

Ei= difference in zero point energies of reactants and transition state structures(J mol-1)

kb =Boltzmann’s constant= 1.38x10-23 J K-1

h= Planck’s constant= 6.63x10-34 J s

T= 298 K

R= Universal gas constant=8.314 J K-1 mol-1

 22

On solving the above equation for a second order reaction, the rate constant value

is obtained in L mol-1 s-1 upon multiplying by a unit concentration term.

The free energies in Gaussian 03 are evaluated from the vibrational frequency analysis,

which is in turn used to determing the partition function based on the harmonic oscillator

model. Therefore, the underlying assumption in this analysis is that the second derivative

matrix is evaluated at a point on the potential energy surface where the gradient is zero.

As such, since the gradient is zero, the coupling between the nuclear degrees of freedom

and the molecular orbital coefficients can be ignored.

When using geometry constraints, the non-zero forces are ignored while

evaluating the optimization criteria. As a result, the energy values change and these

changes cannot be measured legitimately with the implementation of geometry

constraints during optimization. Hence for the thermodynamic calculations, individual

intermediate structures were considered with the entering OH- and leaving H2O

molecules with no geometry constraints on the NiOOH molecule. . For the chemical

oxidation mechanisms no geometry constraints were placed on the system.

 23

Chapter 4 : ELECTRO OXIDATION MECHANISMS

The urea electro-oxidation reactions are as follows12:

Anode: CO(NH2)2(aq) + 6OH-→ N2(g) + 5H2O(l) + CO2 (aq) + 6e- (4.1)

Cathode: 6H2O (l) + 6e-→ 3H2(g) + 6OH- (4.2)

Overall: CO(NH2)2(aq) + H2O(l) → N2(g) + 3H2(g) + CO2 (aq) (4.3)

The anodic reaction is proposed to be taking place on nickel which undergoes

oxidation according to the following reaction in an alkaline medium:

Ni(OH)2(s) + OH- → NiOOH(s) + H2O (l) + e- (4.4)

Within this context the objective in this study is to use Density Functional Theory

(DFT) methods to predict the mechanism and rate determining step of the anodic urea

oxidation reaction on the NiOOH surface. This study is significant in order to understand

and improve overall efficiency of the experimental process of urea electro oxidation. In

order to predict the reaction mechanisms, the electronic energy barriers for the

elementary steps were estimated. Based on these steps, three reaction mechanisms have

been predicted. The proposed reaction mechanisms are as shown in Table 2. To

summarize the pathways, the first step involved the adsorption of urea onto the NiOOH

catalyst, and was common for all three mechanisms. From here onwards, path 1

demonstrated the initial loss of protons from the amino group H1-N1-H2, while path 2

involved the initial loss of protons from the second amino group H3-N2-H4. In path 3,

the amino groups bonded together by the rotation of the group H1-N1-H2 towards N2-

H3, whereas in paths 1 and 2 this rotation takes place only after the elimination of all

protons from the adsorbed species.

 24

After the withdrawal of all the protons of urea by the approaching hydroxyl ions in steps

2 to 6, the final adsorbed structure at the end of step 6 is identical for all the pathways,

rendering a common mechanism from step 7 onwards. These steps have been discussed

in further detail later.

Solvent effects have been excluded as a first approximation. The calculation of

rate constants have been carried out using partition functions obtained from the transition

states and reactants to estimate the rate constants and hence predict the rate limiting step,

as will be discussed in detail later. The initial, transition and final states for all the

reaction pathways are shown in Table 4.1. Each reaction step is illustrated with four

figures: the first structure (a) is the optimized geometry for the initial state. The second

(b) and third figures (c) are the transition and final states respectively.
 25

Table 4.1: Proposed reaction mechanisms for urea electro oxidation reaction

Steps Path 1 Path 2 Path 3

1
CO (NH2)2 + M → [M.CO (NH2)2]ads
[M.CO(NH2)2]ads + OH-
2 [M.CO(NH2)2]ads + OH- → [M.CO(NH2.NH)]ads
→ [M.CO(NH2.NH)]ads
+H2O + 1e-
+H2O + 1e-
[M.CO(NH2.NH)]ads M.CO(NH2NH)ads +
3
+OH- → [M.CONH2N]ads OH-→ [M.CONH2.N]ads Not an Elementary Step
+ H2O + 1e- + H2O
[M.CO.NH2NH]ads +
[M.CO(NH2N)]ads + OH- [M.CO(NH2.N)]ads +
4 OH-→
→ [M.CONHN]ads + H2O OH-→ [M.CONHN]ads
[M.CONH.NH]ads +
+ 1e- + H2O + 1e-
H2O + 1e-
[M.CONHN]ads +OH- [M.CO.NHN]ads + OH- [M.CO.NHNH]ads + OH-
5
→[M.CO.N2]ads +H2O → [M.CO.N2]ads + H2O → M.CO +NH.N + H2O
+1e- + 1e- + 1e-
[M.CO.NHN]ads + OH-
6
Not an Elementary Step → M.CO.N2 + H2O +
1e-
7
[M.CO.N2]ads + OH-→ [M.CO.OH]ads + N2 + 1e-
8
[M.CO.OH]ads + OH-→ [M.CO2]ads + H2O + 1e-
9
[M.CO2]ads→ M + CO2

4.1 Reaction Mechanism Path 1

Step 1

Figure 4.1 shows the first step of the reaction: adsorption of urea onto NiOOH by

the following reaction:

CO(NH2)2 + M → [M.CO (NH2)2]ads (4.5)

M is the catalyst NiOOH. The Gibb’s free energy was calculated as the sum of

energies of the two separate structures of NiOOH and urea. b shows the Transition State
 26

(T
TS) whereass c illustrattes urea adsoorbed onto niickel from oxygen
o (O2) as the site of
o

addsorption. The
T interactioon of NiOOH
H with urea changes
c the NH2 (H4-N2-H3) bond

anngle in c, which
w u moleculle is 118.8o and
in the case of the urea a in the finnal structuree

w NiOOH,, it decreasess to 109.2o. The differennce in structuures betweenn the transitiion

with

sttates and thee final products is the varriation the Ni-O2-C

N bonnd angle whicch is 97.55o in

thhe transition state and 1000.58 degreees in the finaal structure. The
T rate connstant calculaated

foor this reactiion was 6.81 s-1.

(a) (b)

(c)

F
Figure 4.1: Initial state (a) Transitioon state (b) and
a Final struucture (c) foor Equation 4.5
4
 27

(a) (b)

(c)

nitial state (aa), transition state (b) andd final structture (c) for Equation
Figure 4.2: In E 4.6

Step 2

Figuree 4.2 illustraates the initiaal (a) transitiion state (b) and the finaal structure (cc) for

thhe following
g reaction:

M.CO(NH2)2]ads + OH - →[M.CO(N
[M → NH2.NH)]ads +H2O + 1e- (4.6)

In the initial structure the N1--H1 bond lenngth for the dissociating
d proton is 1.002Å

w
whereas in th
he TS, it increases to 1.122Å. The N2--C distance is
i noted as 1.59Å and the

N
N2-Ni bond length
l is 1.922 Å .The rate constant foor this reactiion was calcuulated as

2.7x1011 L mol
m -1 s-1.
 28

Step 3

In step 3 of path 1as shown in Figure 4.3, the NH2 attached is deprotonated by the

approaching OH-, according to the following reaction:

[M.CO(NH2.NH)]ads +OH- → [M.CONH2N]ads + H2O + 1e- (4.7)

Due to the vacant site on N1-H2, it serves as a point of attachment for the free

OH- ion in the initial optimized structure (Figure 4.3a). The N1-(O4H6) bond length in

the initial structure is 1.44 Å, N1-H2 being 1.02 Å. In the TS (Figure 4.3b), H is 1.29 Å

away from N. This OH- then withdraws a proton to leave the system as water.

Subsequently, the N1-C bond becomes shorter in the final structure (1.29 Å) versus the

initial structure (1.43Å). The rate constant for this reaction is 2.8x10-23 L mol-1 s-1.
 29

(a) (b)

(c)

Figure 4.3: In
nitial state (aa), transition state (b) andd final structture (c) for Equation
E 4.7

Step 4

In step
p 4, the folloowing reactioon occurs:

N ads + OH-→ [M.CONH

M.CO(NH2N)]
[M HN]ads + H2O + 1e- (4.8)

W
When H- approachees the secondd NH2 (H3-N
the OH N2-H4) grouup in Figure 4.4a, it pullss

aw
way the entiire NH2 grouup towards it (O4-N2: 1..44 Å, N2-H
H4: 1.02 Å). In the transiition

sttate the proto wards OH-, and the NH (N2-H3) grooup reattachhes back to nickel
on moves tow n

ass shown in th
he final statee (Figure 4.44c). N2-H3 bond
b length in the TS inccreases to 1..13

onstant for this reaction in Equation 4.8 was calcculated to bee 1.1x10-15
Å The rate co
Å.

L mol-1 s-1.
 30

(a) (b)

(c)

nitial state (aa), transition state (b) andd final structture (c) for Equation
Figure 4.4: In E 4.8

Step 5

p 5 (Figure 4.5),
In step 4 similar to step 3, duue to a vacannt site on NH O -
H (N2-H3), OH

O4-H6) adso
(O orbs onto thee surface, acccepts a protoon and detacches as waterr according to
t

thhe following
g reaction:

M.CONHN]ads +OH-→[M.CO.N2]adds +H2O +1e-

[M (4..9)

The O4-N2,
O N2-N
Ni and N2-H
H3 bond lengtths in the iniitial state aree 1.43Å, 1.844Å

annd 1.03Å resspectively (F

Figure 4.5a).. In the TS, the
t N2-H3 distance
d increeases to 1.155Å.

Inn the final sttate, as obserrved in step 3 before, thee N2-Ni bonnd length deccreases to 1.559Å.

T rate consstant for this reaction froom Equation 4.9 is 2.7x10-24 L mol-1 s-1.
The
 31

(a)

(b) (c)

Figure 4.5: In
nitial state (aa), transition state (b) andd final structture (c) for Equation
E 4.99

Step 6

From step 5 (Figuure 4.5c), it is evident thaat the two N (N1 and N22) atoms are at a

siignificant distance from each other, thus preventting the form

mation of N2 and the

suubsequent deesorption off N2 from thee catalyst’s surface.

s In orrder to faciliitate the bondd

foormation bettween the tw

wo atoms, steep 6 was inclluded whereein the diheddral angle

Ni-C-N1 waas changed frrom -177.75o to -0.24o. As

between N2-N A can be seeen from the final

sttructure in th
his step, therre is a bond between
b the two Ns (Figgure 4.6c) whhich will enaable

N2 formation as can be seeen later. Aftter having doonated all itss protons to the
t approachhing

OH- ions, the remaining steps

O s (7, 8, and
a 9) are thee same for both parts 1 and
a 2.
 32

(a) (b)

(c)

Figure 4.6: In
nitial state (aa), transition state (b) andd final structture (c) for re-arrangeme
r ent of

nitrogen atom
ms

Step 7

In step
p 7 (Figure 4.7),
4 H- ion is adsorbed on thee surface whhile
the appproaching OH

thhe N2 is deso
orbed simultaneously wiith the follow
wing reactionn:
-
[
[M.CO.N2]ad M.CO.OH]adds + N2 + 1e-
ds + OH → [M (4.110)

O - gets adsoorbed onto carbon

The OH c whereeas the N2 molecule
m getss desorbed frrom

nickel. The raate constant for this step is 7.3 x108 L mol-1 s-1.

Step 8

n reaction in step 8 (F
The next Figure 4.8) iss as follows:
- -
[
[M.CO.OH]a + OH → [M.CO2]ads + H2O + 1e
ads (4.111)
 33

The last approaching OH- gets adsorbed onto nickel. The Mulliken charge on Ni

reduces from 0.415 in the initial state (Figure 4.8a) to 0.372 in the final state (Figure

4.8c). As a result of this, Ni exhibits a tendency to form a bond with O4, which loses a

proton(H6) to the detaching OH (O5-H7). The rate constant for this step is 1.6 L mol-1 s-1.

Step 9

The final state is CO2 (O1-C-O4) adsorbed onto NiOOH. This gets desorbed in the

final step (Figure 4.9) as follows:

[M.CO2]ads→ M + CO2 (4.12)

The rate constants for the step is 4.3x10-65 L mol-1 s-1 respectively.
 34

(a)
( (b)

(c)

Figure 4.7: In
nitial state (aa), transition state (b) andd final structture (c) for Equation 4.10
 35

(a) (b)

(c)

nitial state (aa), transition state (b) andd final structture (c) for E
Figure 4.8: In Equation 4.11
 36

(a) (b)

(c)

Figure 4.9: In
nitial state (aa), transition state (b) andd final structture (c) for Equation
E 4.12

4.2 Reaction Mechhanism: Pathh 2

Step 1

This step
s is comm
mon for all paathways.

Step 2

In an alternative mechanism
m f step 2, wee consideredd the possibility of the NH
for N 2

H- ion (Figurre 4.10)

atttached to niickel (H3-N22-H4) donatiing its protons to the OH

acccording to the
t followinng reaction:

M.CO(NH2)2]ads + OH- → [M.CO(N

[M NH2.NH)]ads +H2O + 1e- (4.13)
 37

The kinetics
k of thiis step impliied it was fasster than patth 1as the ratte constant value
v

iss 1.38x1017 L mol-1 s-1 veersus the steep 2 of path 1 with a ratee constant vaalue of 2.7 x11011

L mol-1 s-1. Th
his is most likely
l due to the positionn of the OH- molecule whhere it can

obbtain an H from
fr either N1
N or N2 as shown
s in thee transition state.
s T the two N2-
In the TS,

H bond leng
H3 gths are 1.1Å
Å and N2-H44 is 1.15Å. The
T initial strructure (Figuure 4.10a) iss the

saame as consiidered for paath 1. The traansition state and final structures
s aree as shown in

Figure 4.10b and Figure 4.10c

4 respecctively.

(a) (bb)

(c)

Figure 4.10: Initial

I state (a),
( transitionn state (b) annd final struccture (c) for Equation 4.13

Step 3

The reeaction in thhis step is as follows:

M
M.CO(NH N ads + OH-→ [M.CONH
2NH) H2.N]ads + H2O + 1e- (4.114)
 38

T N2-H4 bond lengths in the initiall structure (F

The Figure 4.11bb) and TS (Fiigure 4.11c) are

1.02Å and 1.2 r constantt is 2.3x10-21 L mol-1 s-1.

28Å respectiively. The rate

(a) (b)

(c)

Figure 4.11: Initial

I state (a),
( transitionn state (b) annd final struccture (c) for Equation 4.14

Step 4

Next,, the approacching OH- taakes up a hyddrogen from

m the second NH2 (H1-N1-

H group according to thhe followingg reaction:

H2)

[M N)]ads + OH-→ [M.CON

M.CO(NH2.N NHN]ads + H2O + 1e- (4.15)

It can also be seenn that due to presence off excess electrons on N, it

i forms a rinng

liike structure with nickel and oxygenn. The N-H bond

b length increases
i froom 1.02Å in the

innitial state to
o 1.05Å in thhe final state. (Figure 4.112) The rate constant forr this step waas

caalculated as 4.1 x107 L mol

m -1 s-1.
 39

(a) (b)

(c)

Figure 4.12: Initial

I state (a),
( transitionn state (b) annd final struccture (c) Equuation 4.15

Step 5

p 5 of path 2 the NH (H1-N1) groupp loses its lasst proton to the

In step t approachhing

OH- with the following reeaction:

O

M.CO.NHN]ads + OH-→ [M.CO.N2]ads + H2O + 1e-

[M (4.16)

The N-H
N bond lenngth changess from 1.02Å
Å to 1.14Å between
b the initial
i and

trransition stattes (Figure 4.13).

4 The reemaining struucture is idenntical to the one obtained in

sttep 6 of path
h 1 where rottation of nitrrogen needs to be accom
mplished in order
o to faciliitate
 40

desorption off the N2 moleecule. The raate constant for this step is 8.8x1015 L mol-1 s-1.

From here on
n the steps foor paths 1,2 and
a 3 are ideentical.

(a) (b)

(c)

Figure 4.13: Initial

I state (a),
( transitionn state (b) annd final struccture (c) for Equation 4.16
 41

4.3 Reaaction Mechhanisms: Pathh 3

Steps 1 and 2

They are the samee as path 2.

Step 3

p 3 of path 2,
In step 2 NH2 (H1-N
N1-N2) grouup detaches from
f carbon and attaches to

N (N2-H3),, forming a cyclic

NH c structuure as shownn in Figure 4.14.
4 This faacilitates

desorption off N2 in the laater steps witthout the neeed to rotate the
t N-atoms towards eacch

otther.

(a) (b)

(c)
 42

Figure 4.14: Initial

I state (a),
( transitionn state (b) annd final struccture (c) for rearrangemeent

of amine grou
ups

Step 4

In the next step 4,, (Figure 4.15) the NH2 group

g loses a proton to thhe approaching

OH- ion, form

O ming water according
a to the reaction:

[M N ads + OH-→ [M.CON

M.CO.NH2NH] NH.NH]ads + H2O + 1e- (4.17)

As sho
own in the TS H- withdraw
T (Figure 4.15b), there is a possibillity of the OH wing a

prroton from either

e of the amine groupps. As a resuult, this is thee fastest stepp in this pathhway,

thhe rate consttant being 1.12x1017 L/m

mol.s. The N1-H2 bond lengths
l for thhe dissociatiing

prroton are 1.0

02Å and 1.266Å in the iniitial (Figure 4.15a) and transition
t staate (Figure

4.15b) respecctively. The N1-N2

N bondd length decrreases from the
t initial to final step frrom

1.43Å to 1.39
9Å.

(a)) (b) (c)

Figure 4.15: Initial

I state (a),
( transitionn state (b) annd final struccture (c) for Equation 4.17
 43

Step 5

Thereafter, the next approaching OH- takes up a proton from the –N1H1 group

(Figure 4.16). The rate constant for this step is 2.5x10-4 L mol-1 s-1 in the following

reaction:

[M.CO.NHNH]ads + OH-→ M.CO +NH.N + H2O + 1e- (4.18)

 44

(a) (b)

(cc)

Figure 4.16: Initial

I ( transitionn state (b) annd final struccture (c) for Equation 4.18
state (a),

Step 6:

p 6, (Figure 4.17) when the approachhing OH- takkes up the laast proton
In step

acccording to the
t followinng reaction:

M.CO.NHN]ads + OH- → M.CO.N2 + H2O + 1e

[M (4.19)

The fiinal structuree is the samee as the one obtained froom path 1 steep 6. In this

pathway sincee the nitrogeen atoms bouund togetherr initially in step

s 3, it neggates for theiir

rootation towaards each othher as in pathh 1. The N2-H3 bond lenngths for the initial (Figuure

4.17a) and traansition statees (Figure 4..17b) are 1.001Å and 1.022 Å. The N1-N2 bond length
 45

becomes shorrter in the finnal step (1.43Å) from initial step (1.223Å). The raate constant for

i 3.6x10-7 L mol-1 s-1 froom Equationn 4.9. The nitrogen

thhis reaction is n atom
ms are in thee

vicinity of each other in this

t step, hennce eliminatiing the needd for rotationn as was requuired

inn path 1. Thu

us this path has
h least resiistance as coompared to path
p 1.

Steps 7, 8 an
nd 9

Thesee subsequentt elementary steps will now be same as in path 1.

(a) (b)

(c))

Figure 4.17: Initial

I state (a),
( transitionn state (b) annd final struccture (c) for Equation 4.17
 46

The free energies values as well as the rate constants for the steps for the different

pathways are summarized in Tables 4.2 and 4.3.

As can be seen from the rate constant values, the desorption of CO2 from NiOOH

is the rate limiting step with a value of the order of magnitude of -65. This conclusion is

supported by the fact that the urea electrolysis reaction rate decreases with time which

can be attributed to a surface blockage of the catalyst when a build up of CO2 takes place

over a period of time8. Thermodynamic calculations also suggest the largest contribution

to the free energy change of the reaction is from the last step. The total free energy

change (ΔG) required is 1227.7 kJ mol-1, whereas the requirement for CO2 desorption

alone is 1242.2 kJ mol-1. Using this value of ΔG, the theoretical value of of the cell

potential was calculated using the Nernst Equation

ΔG=-nFEocell (4.20)

where,

ΔG= Change in Gibbs Free Energy (kJ mol-1)

n= Number of electrons transferred per mole of reactant

F= Faraday’s Constant (96485 coulombs mol-1)

Eocell= Standard Potential (V)

The calculated Standard Potential was calculated as -2.12V at 298 K and 1

atmosphere pressure. The difference between this calculated potential and the theoretical

potential versus SHE8 of -0.46V can be attributed to two main factors. Firstly, in this

system one NiOOH site per molecule of urea has been considered. This system of single

molecule interactions limits the available active catalyst sites per molecule of urea. As a
 47

result the overall energy required to desorb the final product CO2 is expected to be higher

in such a system, as compared to systems with larger NiOOH cluster sizes where a

greater number of catalytic sites are available per molecule of reactant. This in turn

explains the higher value of calculated standard potential. Secondly, gas phase

calculations have been performed without using solvent effects in order to simplify the

system. This has also possibly accounted for deviation in calculation of cell potential.

However, since the objective of this study was to gain a relativistic view of the kinetics of

the elementary steps, this has been well accomplished using a considerably simple model

of single molecule gas phase interactions.

Furthermore, we considered the possibility of other causes of surface blockage,

mainly from the preferential adsorption of OH- onto the surface of NiOOH. The binding

energies of CO2 and OH- calculated to be 9.2 kJ mol-1 and 18.0 kJ mol-1 respectively. This

suggested that in excess of OH- ions, the hydroxyl group is more preferentially adsorbed

onto the catalyst’s surface than CO2. This competition between adsorbed OH- and CO2 on

the catalyst’s surface leads to an increased tendency of surface blockage which could

further explain the decreased rate of reaction with time.

 48

Table 4.2: Sum of free energies for all the intermediate steps

Reactions ∆G (kJ mol-1)

CO (NH2)2 + M → [M.CO (NH2)2]ads 66.2

[M.CO(NH2)2]ads + OH- → [M.CO(NH2.NH)]ads +H2O + 1e- -28.9

[M.CO(NH2.NH)]ads +OH- → [M.CONH2N]ads + H2O + 1e- -185.1

[M.CO(NH2N)]ads + OH-→ [M.CONHN]ads + H2O + 1e- 75.4

[M.CONHN]ads +OH-→[M.CO.N2]ads +H2O +1e- -178.2

[M.CO.N2]ads + OH-→ [M.CO.OH]ads + N2 + 1e- 392.7

[M.CO.OH]ads + OH-→ [M.CO2]ads + H2O + 1e- -156.6

[M.CO2]ads→ M + CO2 1242.2

Total 1227.7
 49

Table 4.3: Kinetics of the reaction pathways and rate constants for intermediate steps

Rate Constants (L mol-1 s-1)

Steps Path 1 Path 2 Path 3
1 6.8

2 2.3x1011 1.38x1017

Not an Elementary
3 2.8x10-23 2.3x10-21 Step

4 1.1x10-15 4.1x107 1.1x1017

5 2.7x10-24 8.8x1015 2.5x10-4

6 Not an Elementary Step 3.6x10-7

7 7.3x108
8 1.6
9 4.3x10-65 (rds)

4.5 Conclusion

Based on the calculations summarized in Table 4.3, it can be deduced that

kinetically, the last step, i.e. desorption of CO2 from the catalyst’s surface is the rate

limiting step. This indicates the occurrence of surface blockage in the presence of a larger

number of reacting molecules of urea than what is considered here. Thermodynamic

calculations ( Table 4.2)also suggest a large contribution to the free energy change

occurring from the last step. Total free energy change required is 293.1 kcal mol-1,

whereas the requirement for CO2 desorption alone is 296.7 kcal mol-1. Using the free
 50

energy, the theoretical value of the cell potential was calculated to be -2.12V. The

difference between this theoretical and experimental value8 of -0.46V obtained can be

attributed to the limitation of using gas phase calculations as well as single molecule

interactions in the system.

Also, the path of least resistance is path 2, wherein the NH2 migrates to bond with

the NH group initially in step 3, before the remaining proton transfer could take place. As

a result of this migration, it involves no further need to rotate the N molecules towards

each other to bring about N2 desorption, as the atoms are already in the vicinity of each

other. This makes path 2 the preferred pathway. However, even if the reaction progresses

via any given mechanism, the rate limiting step, i.e, desorption of CO2 is common to all

the mechanisms.
 51

Chapter 5 : CHEMICAL OXIDATION MECHANISMS

The objective of this study was to investigate the thermodynamics and kinetics of

the urea decomposition reactions occurring on NiOOH. The first consideration was urea

adsorbed onto the surface of NiOOH, and secondly the inclusion of a hydroxide ion in the

system was considered, to investigate the catalytic effects of OH- in the reaction.

5.1 Different Orientations of Urea towards NiOOH

The electrophilic atoms of urea were oriented towards the nucleophilic atoms of NiOOH

and vice versa (Figure 5.1). The configurations obtained are tabulated along with their

binding energies Table 5.1. In Figure 5.1 a, the interaction of Ni with N1 was considered,

wherein no significant interaction between the two species was observed. In Figure 5.1b

the interaction of Ni with O1 was considered which resulted in a similar output of

NiOOH separated from urea as in Figure 5.1a. In Figure 5.1c, double atomic interactions

of Ni with N2 and OH with C were considered. The resulting output as shown consisted

of detached ammonia and isocyanic acid attached to NiOOH. In Figure 5.1d, Ni

interacted with N2 while O2 interacted with C. The resulting structure has urea attached

to NiOOH through the point of attachment of carbon. In Figure 5.1 e the interaction of Ni

with N2 and OH- with C was considered, which resulted in breakage of OH from NiOOH

and attachment of Ni-O to urea.

The binding energies of structures in Figure 5.1 b and Figure 5.1 d were the least

in the group, suggesting that these structures were most likely to undergo dissociation.

Since structure in Figure 5.1 d shows a more plausible scenario of multiple atomic
 52

innteractions (b
between Ni--N and O-C)), it was conssidered for thhe complete dissociationn

m
mechanism of NiOOH wiith urea.

(a) (b)

(c)
( (d))

(e))

Figure 5.1: Optimized

O strructures for different
d orieentations of urea towardds NiOOH
 53

Table 5.1:Binding Energies of different orientations of urea towards NiOOH

Binding Energies (kJ mol-1)

a. 11.7

b. 5.9

c. 11.3

d. 8.3

e. 12.6

5.2 Urea decomposition with NiOOH

The proposed reaction mechanism for dissociation of urea in the presence of

NiOOH is as follows:

(NH2)2CO + NiOOH Æ (NH2)2CO. NiOOH (5.1)

(NH2)2CO. NiOOH Æ HNCO.NiOOH + NH3 (5.2)

The optimized reactants, products and transition states are shown in Figure 5.2

and Figure 5.3. Upon attachment to NiOOH, the urea molecule which initially resides in

a single plane has now been changed as the Hs on the amides bend closer to each other

and out of the original plane. The N1-C-N2 bond angle changes from 115.4o in urea

(Figure 5.2a) to 110.4o in intermediate 1(Figure 5.2b). The H1-N1-H2 and H3-N2-H4

bond angles in urea are 118.8o and they reduce in intermediate 1 from 109.2o to 107.9o

respectively. Between the transition state TS I in Figure 5.3a, and intermediate 1(Figure
 54

5.2b), the Ni--O-C angle changes

c m 97.6o to 1000.6o. There is no signifiicant differennce
from

inn the other parameters.

In step
p 2, N2 donaates its protoon to the leavving ammonnia molecule which detacched

inn the final prroduct at a distance of 2..02 Å from NiOOH

N (Figgure 5.2c). Thhe isocyanicc acid

reemains boun
nd to NiOOH
H from the pooints of attacchment of Ni
N and O. Thee Ni-N2 bonnd

annd C-O2 bon

nd lengths arre 1.87 Å annd 1.36 Å, reespectively. NH3 is seenn to rotate aroound

thhe bound HC
CNO group at
a the Ni-N1 distance off 2.01 Å.

The values of ratee constants for

fo the forwaard reactions were calcullated as k1= 6.81
6

s-1
-
10-6 s-1, indiccating that libberation of ammonia
, k2= 1.54x1 a is the
t rate limiting step in this
t

reeaction. Table 5.2 showss the changes in free eneergy in the tw

wo steps of thhe reaction.

(a) (b)

(c)

Figure 5.2: Optimized

O strructures for Equations
E 5..1 and 5.2
 55

(a) (b)

Figure 5.3: Optimized

O Transition Stattes for Reacttions 2 and 3

Table 5.2: Free Energyy differencess for equatioons 5.1 and 5.2
5

Sttructures Freee energies chhanges (kJ mool-1)

Equuation 5.1 -666.9

Equuation 5.2 -2009.3

O
Overall -2776.3

5.3 Urea and NiOOH

N o OH- ion:
in the presence of

n OH- was opptimized witth NiOOH, itt resulted in the adsorptiion of the
When

hyydroxide ion
n onto Ni as shown in Fiigure 5.4. Thhe output struucture was then
t further

opptimized witth urea.

T proposed
The d reaction meechanism is as follows:

(N
NiO.OHOH))ads + CO(NH
H2)2→ (Ni(O
OH)3.CONH.NH2)ads (
(5.3)

(N
Ni(OH)3CON
NH.NH2)ads →(Ni(OH)3.C
CNO)ads + NH
N 3 (5.4)
 56

Figure 5.4: Adsorption

A off OH- onto NiOOH
N

(a) (b)

(c)
(

Figure 5.5: Optimized

O strructures for Equations
E 5..3 and 5.4.

Figuree 5.5a illustrrates the optiimized reacttants for Equuation 5.3 annd 5.4. The N1-
N

N distance iss 2.06Å. In thhe intermediiate structuree (Figure 5.55b), the ureaa molecule
Ni

unndergoes rottation to such that both NH

N 2 groups face downw
wards. Due too the close

prroximity of N1-H1
N to O2, O2 withdrraws the prooton from N11 while N1 bonds
b to Ni at
a the

saame time. Th
he N1-Ni boond length reeduces to 1.996Å. The N11-C-N2 bondd angle increeases
 57

frrom 111.1o in the reactannts to 115.8o in the interm

mediate due to the N1-N
Ni bonding. In
I

thhe transition state for this step (Figurre 5.6a), the urea molecuule is not rottated, and thee

prroton H5 facces away froom the N2 am

mine group.

TS I (aa) TS II (b))

Figure
F 5.6: Transition
T Sttate Structurres for Equattions 5.3 andd 5.4

In equ
uation 5.4, am
mmonia is formed
fo and desorbed,
d leaaving CNO- still adsorbeed

onnto Ni(OH)3 (Figure 5.5c) at a distannce of 2.09 Å from O2. The

T Ni-N1 distance
d does not

chhange signifficantly at 1.95Å. The Nii-N1-C bondd angle is 1334.4o. The traansition statee for

thhis step (Figu

ure 5.6b) illuustrates the displacemen
d nt of proton H2
H between the two amiine

grroups. H2 iss at a distancce of 1.28 Å from the leaaving NH grooup and 1.322Å from the

H2 group. The rate constaant calculatioons yield thee rate constaant for reactioon
acccepting NH

5.3 as 3.02 x 104 L mol-1 s-1 and for reeaction 5.4 as

a 1.37x10-266 L mol-1 s-1. In this casee, as

inn the previou

us mechanism
m too, the ellimination of ammonia is
i the rate deetermining sttep.

T reaction profile
The p as a function
f of the
t reaction coordinates is shown in Figure 5.8. The

frree energies for the two steps are givven in Table 5.3.
 58

Table 5.3: Free Energy differences for reactions 5.3 and 5.4

Structures Free energy changes (kcal mol-1)

Equation 5.3 -581.9

Equation 5.4 -16.7

Overall -598.7

5.4 Conclusion

The free energy differences between the reactants and products in the both the

mechanisms suggest that the reaction occurs spontaneously. The free energy difference

between the two steps is higher in the presence of OH- rather than without it, suggesting

that the reaction occurs more spontaneously in the presence of OH-. This is validated by

experimental results, as there are traces of ammonia present as a result of the urea

decomposition reaction.
 59

Chapter 6 : EXPERIMENTAL

The experimental section is a brief study carried out in order to study the effect of

varying concentrations of KOH and urea on the current density obtained. The urea electro

oxidation reaction has been analyzed by conducting potentiodynamic tests with a rotating

disk electrode. The rotating disk electrode offers several advantages over stationery

electrode experiments. With the disk in constant motion, reaction rates are not diffusion

limited. Hence it throws light on the nature of the reaction taking place37. With

conventional experiments conducted using a rotating disk electrode, a steady state current

profile is obtained with changing potentials. However this is not the case with the urea

electro oxidation reaction, where reactions of a more complex nature seem to be going on

at the surface of the electrode, as will be discussed later.

The different operational parameters studied are the concentration of KOH, urea

and temperature effects on the current density of the reaction. Preliminary tests were

conducted to identify the lowest possible concentrations of KOH at which a response is

obtained. Once the lowest concentration was established, the current density at 5 levels of

concentration of KOH tested for 3 levels of concentration of urea were carried out at

room temperature.

6.1 Experimental Methods: Electroplating and Preliminary Results

Catalyst preparation was performed in two stages: one for the preliminary tests

and another for the main set of experiments. The chemicals were obtained from Alfa

Aesar or Fisher Scientific. Electroplating was carried out in a 200 mL beaker at 45° C
 60

against a platinum foil counter electrode. The bath composition was as follows:

NiSO4.6H2O (280 g L-1), NiCl2.6H2O (40 g L-1), H3BO3 (30 g L-1).

The Rotor and Motor for the Rotating Disk Electrode Model 616 were obtained

from Pine Industries. A 5mm diameter Titanium removable disk was fitted into a Teflon

block which was then mounted onto the shaft of the rotating disk.

6.2 Potentio-dynamic Tests

In the preliminary study, a 2 cm by 2 cm Titanium foil electrode was electroplated

with nickel in the plating bath described above. The electro deposition was carried out at

-0.7 Volts versus Ag/AgCl electrode at 45o C for 15 minutes giving a catalyst loading of

100 mg, effectively 12.5 mg cm-2.. This nickel plated titanium electrode was used to

determine lowest concentration of KOH at which a response was obtained. Urea electro

oxidation to determine the response was carried out at room temperature starting with 2

M KOH, decreasing in steps of 0.5 M.

For the second stage, the titanium removable disk electrode of diameter 5 mm was

electroplated with under the same operating conditions as mentioned above in the same

plating bath. Electroplating was carried out again for 15 minutes giving a deposition of

1.5 mg± 0.2 mg, effectively 5.1 mg cm -2. A platinum ring arrangement was used as the

counter electrode around the removable rotating disk working electrode.

The preliminary set of experiments was conducted at 4 levels of KOH

concentration. The concentration of urea was kept constant at 20 g L-1 (composition of

the human urine) and all experiments were performed at room temperature. The 4 levels

of concentration of KOH tested were 1 M, 0.5 M, 0.25 M and 0.1M. This study was
 61

conducted to purely select the lowest concentration at which a response is obtained. The

upper limit of the experiment matrix is set at 5 M KOH.

The second stage of experiments was carried out at five levels of concentration of

KOH and three levels of concentration of urea namely 0.5 M, 1 M, 2 M, 3 M, 5 M KOH.

The speed of rotation of the rotating disk electrode was set at 1000 rpm, with the Hg-

HgO reference With 0.5 M KOH solution, the three levels of concentration of urea were

tested by performing cyclic voltammetry on the Solartron potentiostat. Then the

concentration of KOH was changed and the three concentrations of urea were again

tested. All experiments were performed at room temperature. The scan rate used was

20mV s-1.

6.3 Results and Discussion

Figure 6.1 represents the set of experiments performed initially to determine the

lower set point of KOH concentrations. 4 concentrations of KOH were tested starting

with 0.1 M. There was no response peak at 0.1 M. The lowest concentration of KOH that

gave a response was 0.25 M. There was not a significant difference between the

maximum current obtained with 0.25 M and 0.5 M. Hence 0.5 M was chosen as the lower

set point.
 62

Figure 6.1: Preliminary experiment. Different concentrations of KOH at 20g L-1 urea to

determine lower setpoint.

The peaks given in Figure 6.2, Figure 6.3 and Figure 6.4 were obtained for

different concentrations of KOH at different urea concentrations. Baseline KOH

represents a solution with 1M KOH with no urea present. It is evident from all three

figures that the current density corresponding to the peak is the highest in the case of 5M

KOH. There is not a significant increase in the current density in case of 1 M, 2 M and 3

M KOH for all three concentrations of urea used.

 63

Figure 6.2: Urea concentration of 5 g L-1 varying KOH concentrations. Scan rate: 20mV

s-1. Speed of rotation: 1000rpm.

Figure 6.3: Urea Concentration of 10 g L-1 with varying KOH concentrations. Scan Rate:

20mV s-1. Speed of rotation 1000rpm.

 64

Figure 6.4: Urea concentration of 20 g L-1 with varying KOH concentrations. Scan rate

20mV s-1. Speed of rotation 1000 rpm.

6.4 Conclusion

This experimental study was strongly indicative of the fact that the concentration

of KOH plays a significant role in catalyzing the oxidation reaction. The maximum

current density obtained at 5 M KOH supports the argument that a higher concentration

of KOH is more favorable towards the oxidation reaction. However, as can be seen from

the oxidation peak and the rapid decrease of current from potentials of 0.55V to 0.7V,

which is uncharacteristic of rotating disk electrode experiments, it is an indication of an

adsorption-desorption reaction occurring on the electrode surface. There is a possibility

of adherence of CO2 or the OH- onto the NiOOH surface which causes this rapid rise and

fall of the electrode current.

 65

Chapter 7 : CONCLUSIONS AND RECOMMENDATIONS

In summary, the electro oxidation reaction mechanisms studied indicate the

desorption of CO2 as the rate limiting step with the calculated rate constant value of

4.32x10-65 L mol-1s-1 . The desorption step also contributes to the maximum energy

requirement of the path (1242.2 kJ mol-1). Also based on the kinetics of the reaction,

*CO(NH2)2→ *CO(NH.NH2)→ *CO(NH.NH)→ *CO(NH.N)→*CO(N2) → *CO(OH)

→*CO(OH.OH) →*CO2 has been identified as the preferred pathway among the three

mechanisms. This has been discussed in Chapter 4 as Path 2. In this pathway, the bonding

between the NH2-NH group occurs initially versus the rotation of the nitrogen atoms

towards each other in the later stages as in Path 1. This facilitates easy desorption of the

nitrogen molecule.

Another important finding of this study is the investigation of causes of surface

blockage, mainly from the preferential adsorption of OH- onto the surface of NiOOH.

The binding energies of CO2 and OH- calculated to be 9.2 kJ mol-1 and 18.0 kJ mol-1

respectively. This suggested that in excess of OH- ions, the hydroxyl group is more

preferentially adsorbed onto the catalyst’s surface than CO2. This competition between

the molecules leading to adsorption onto the NiOOH surface leads to an increased

tendency of surface blockage which explains the decreased rate of reaction as time

progresses.

In the chemical oxidation mechanisms, the thermodynamic feasibility of the

reaction mechanisms both without and in the presence of OH- has been discussed.

Change in free energy for the oxidation mechanism without OH- is -276.3 kJ mol-1
 66

whereas with OH- it is -598.7 kJ mol-1. This indicates a greater spontaneity of the

reaction in the presence of hydroxide ions, which is known to catalyze the reaction. In

both the reaction mechanisms, the desorption of ammonia is the rate limiting step. In

mechanism 1 it was calculated as 1.54x10-6 s-1 and in mechanism 2 it is 1.37x10-26

L/mol.s.

The experimental potentio-dynamic tests carried out with 3 levels of

concentration of KOH (0.5 M, 1 M, 2 M, 3 M, 5 M) indicate a significant increase in

current density of the anodic reaction with the highest KOH concentration in the matrix

of 5M in case of all three levels of concentration of urea of 5, 10 and 15 g L-1. There is no

significant difference in current densities for the lower concentrations of KOH. This is in

agreement with the modeling results which also indicate a greater favorability of the

reaction in presence of OH-.

After the role of OH- and the rate limiting step in the oxidation mechanism has

been established with this study, it is now recommended to look into improvements in the

rate constant approximations with inclusion of solvent effects in the system. Greater basis

sets can also be used to carry out similar calculations. At the same time, an experimental

model should be developed to calculate experimentally the kinetic parameters of the

model which can then be compared to the theoretical values.

 67

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 72

APPENDIX A

SUPPORTING INFORMATION FOR ELECTROCHEMICAL OXIDATION OF UREA

Figure 4.1a.
Cartesian Co-ordinates
C -1.82316000 -0.24239000 0.01975200
O -2.55328600 -1.13695200 -0.35074500
N -1.97383000 1.09072400 -0.14353600
H -1.12406800 1.67220000 -0.09544600
H -2.72889600 1.37104700 -0.75445700
H -0.59547900 -1.56764400 0.95055800
N -0.60348500 -0.56182000 0.78547000
H -0.59210900 -0.06419400 1.67783600
O 0.67900800 1.75585200 0.08121300
Ni 1.16539200 0.02173500 -0.05718900
H 1.30277400 2.39748300 -0.28939300
O 1.88514900 -1.45208300 -0.29295200

Sum of electronic and zero-point Energies= -545.482798

Number of Imaginary Frequencies= 0

Figure 4.1b.
Cartesian Co-ordinates
C 1.41239600 0.01851800 0.08323000
O 1.81069200 -0.21337200 1.34003300
N 0.38580700 1.16294000 0.06431400
H 0.52624400 1.79385800 -0.72441100
H 0.39711300 1.68465100 0.94067000
H 3.34913000 0.14233900 -0.43878800
N 2.44541400 0.26800800 -0.89024100
H 2.36721100 -0.43278900 -1.62530200
O -2.74998500 0.19414100 -0.05149200
Ni -1.03769300 -0.18616900 -0.08272000
H -3.14380200 0.60065900 0.73432400
O 0.59761700 -1.06873400 -0.19956800

Sum of electronic and zero point Energies= -545.458333

Number of Imaginary Frequencies= 1

 73

Figure 4.1c.
Cartesian Co-ordinates
C 1.41709000 -0.01699400 0.08075200
O 1.83677600 -0.71645200 1.13680100
N 0.39217400 1.04688300 0.49994200
H 0.52026600 1.94794500 0.03881700
H 0.42578200 1.17902500 1.51094400
H 3.22910400 -0.08598300 -0.75036700
N 2.47127100 0.58917500 -0.67591300
H 2.15179700 0.80659800 -1.61984000
O -2.75475400 0.19854100 0.01374500
Ni -1.03883900 -0.13894400 -0.13879000
H -3.16555000 0.21392000 0.89076100
O 0.59040700 -0.92227900 -0.58015900

Sum of electronic and zero point energies= -545.458736

Number of Imaginary Frequencies= 0

Figure 4.2a.
Cartesian Co-ordinates
C 1.20477200 -0.76897600 0.05966100
O 1.85529500 -1.68279900 0.64009700
N 0.30534900 0.14547400 1.01417700
H 0.67818100 1.11212400 1.01899500
H 0.26404500 -0.27581900 1.94032500
H 3.02345900 0.25160400 -0.15776700
N 2.11110400 0.28811100 -0.60411100
H 2.19992300 0.07273300 -1.59702100
O -2.99382400 0.53908400 0.05754000
Ni -1.21216700 -0.12352700 -0.12886100
H -3.44559700 -0.01897600 0.69175900
O 0.21439700 -1.07721100 -0.89684500
H 1.03501000 2.35076700 -0.63881400
O 1.67936100 2.41406100 0.08948300

Sum of electronic and zero-point Energies= -621.290518

Number of Imaginary Frequencies= 1
 74

Figure 4.2b.
Cartesian Co-ordinates
C -1.00853200 0.38715800 0.09992600
O -1.79221700 0.91899500 0.93547700
N -0.00754200 -0.67147100 0.75841700
H -0.18298600 -1.64336300 0.50613300
H -0.02112300 -0.54339800 1.76945600
H -1.93274400 0.22917700 -1.71882000
N -1.64546300 -0.46021200 -1.02067400
H -2.59039100 -0.92884500 -0.63632000
O 3.23163000 -0.62758900 -0.00731400
Ni 1.46783800 0.09830500 -0.10838500
H 3.60446200 -0.30301000 0.81330000
O -0.02117600 1.16827400 -0.52359800
H -3.37570400 -0.00699700 0.54014400
O -3.79058100 -0.70433700 -0.02992300

Sum of electronic and zero-point Energies= -621.287915

Number of Imaginary Frequencies= 2

Figure 4.2c.
Cartesian Coordinates
C -0.98825400 -0.61353200 -0.08341100
O -1.89510300 -0.78725900 -0.99862700
N -0.28348700 0.80947600 -0.17768400
H -0.65390500 1.46341900 0.51023900
H -0.47033000 1.17283700 -1.11154800
H -1.84394100 -1.62838700 1.34744900
N -1.62676500 -0.63177300 1.21994800
H -3.11019500 0.94708400 0.86349900
O 3.17859200 0.75770900 0.16281800
Ni 1.44396400 -0.02770900 0.01353500
H 3.46707600 1.02064700 -0.71205600
O 0.17247500 -1.40458300 -0.13455200
H -3.05429100 0.68477300 -0.58135600
O -3.38897900 1.37822600 0.03403700

Sum of electronic and zero-point Energies= -621.319782

Number of Imaginary Frequencies= 2
 75

Figure 4.3a
Cartesian Coordinates
C 1.45975300 0.00492500 -0.04374900
O 1.52767800 1.10600600 0.53073600
N -1.41977700 1.46060300 -0.65833300
H -2.23479800 1.85756100 -0.17860800
H -0.59904700 1.87629000 -0.20172900
H 2.66707100 -1.60381100 -0.22294400
N 2.69410500 -0.60726300 -0.42678900
O -3.17691400 -0.50928800 0.50907400
Ni -1.36679900 -0.26902300 -0.05115700
H -3.16970400 -0.16791400 1.40415900
O 0.43525600 -0.68025000 -0.39450700
H 3.32800200 0.72784200 0.70572700
O 3.78898500 -0.06150100 0.32771400

Sum of electronic and zero-point Energies= -620.758842

Number of Imaginary Frequencies= 1

Figure 4.3b
C -1.46935900 0.06621100 -0.10310400
O -1.97486000 1.07859000 -0.55952800
N 1.18200300 1.44064700 0.62516000
H 2.09753600 1.89108600 0.53065700
H 0.57108700 1.91237200 -0.05207400
H -3.96278600 -0.92103600 0.31696000
N -1.52080100 -0.91249800 0.73525900
O 3.35823800 -0.33933700 0.00554800
Ni 1.45144900 -0.24042900 -0.04419700
H 3.62261800 0.04461000 -0.83138200
O -0.32334900 -0.66667900 -0.49453300
H -3.89480800 0.50498900 -0.15340800
O -4.54584000 -0.17186100 0.11382100

Sum of electronic and zero-point Energies= -620.682434

Number of Imaginary Frequencies= 2
 76

Figure 4.3c.
C -1.46935900 0.06621100 -0.10310400
O -1.97486000 1.07859000 -0.55952800
N 1.18200300 1.44064700 0.62516000
H 2.09753600 1.89108600 0.53065700
H 0.57108700 1.91237200 -0.05207400
H -3.96278600 -0.92103600 0.31696000
N -1.52080100 -0.91249800 0.73525900
O 3.35823800 -0.33933700 0.00554800
Ni 1.45144900 -0.24042900 -0.04419700
H 3.62261800 0.04461000 -0.83138200
O -0.32334900 -0.66667900 -0.49453300
H -3.89480800 0.50498900 -0.15340800
O -4.54584000 -0.17186100 0.11382100

Sum of electronic and zero-point Energies= -620.698557

Number of Imaginary Frequencies= 1

Figure 4.4a.
C 2.02492500 -0.38489000 -0.00241700
O 1.99230200 0.91605100 0.08180300
N -0.61064000 1.43887000 0.56088100
H -1.36543800 2.04508800 0.88167600
H 0.16339300 1.45952600 1.23586300
N 3.10461800 -1.09422100 0.09749400
O -2.81349600 -0.74968000 -0.07955800
Ni -0.91949600 -0.52005600 0.01063900
H -3.23848300 0.10260600 0.02417000
O 0.86501000 -1.07525700 -0.19354400
H 0.87111100 1.60390300 -0.56236200
O -0.08032800 2.06478900 -0.61762000

Sum of electronic and zero-point Energies= -620.105700

Number of Imaginary Frequencies= 1

 77

Figure 4.4b.
C 2.01170900 -0.35367700 0.00509000
O 2.18295300 0.86382800 0.29183800
N -0.97253500 1.00690500 1.05888200
H -0.90336700 1.85766900 0.31385400
H -0.07156000 1.03695000 1.55617200
N 3.21320000 -0.94561200 -0.18820800
O -2.76489000 -0.75587600 -0.29843000
Ni -0.89091900 -0.51640500 -0.01738600
H -3.16585000 -0.08689400 0.25785900
O 0.92016600 -1.01324400 -0.10412700
H 0.66233400 2.05342800 -0.57228000
O -0.25457200 2.31669100 -0.78853600

Sum of electronic and zero-point Energies= -620.043488

Number of Imaginary Frequencies= 2

Figure 4.4c.
C 1.96280600 -0.43774300 0.00690100
O 2.15911500 0.75955800 0.29045100
N -1.01634500 0.81115600 1.12483600
H -0.52846700 2.35796200 -0.09843000
H -0.07393700 0.78283100 1.55640600
N 3.10837800 -1.22417600 -0.20758200
O -2.82974900 -0.56562900 -0.38717700
Ni -0.95133400 -0.54084800 -0.04215000
H -3.13908700 0.18970600 0.11436400
O 0.85033100 -1.07380200 -0.10819300
H 0.94280400 2.18654700 -0.37593500
O 0.19717400 2.77291100 -0.60488200
Sum of electronic and zero-point Energies= -620.073313

Number of Imaginary frequencies= 1

Figure 4.5a.
C 1.85531900 -0.51445200 -0.04685200
O 2.02630300 0.33721900 0.96322400
N -1.00502600 1.39784300 -0.11606600
H -1.15329900 1.59437300 0.88437800
N 3.14067500 -0.54648500 -0.09955600
O -2.72238400 -0.61415200 0.49622800
Ni -0.91312400 -0.44327300 -0.09154700
H -3.18626000 -0.03964600 -0.11412000
O 0.81996400 -0.96466100 -0.60042600
H 0.91654400 1.69123500 0.19153900
 78

O 0.23974600 2.02820400 -0.43503000

Sum of electronic and zero-point Energies= -619.463527

Number of Imaginary Frequencies= 1

Figure 4.5b.
C -1.80307200 -0.43587900 -0.03111000
O -2.06590800 0.82757900 -0.32615400
N 1.40802000 1.26871100 -0.77548000
H 1.18727100 2.05879800 0.03327100
N -3.05916200 -0.53880500 0.22860600
O 1.84845500 -1.49960600 0.69189800
Ni 0.88835200 -0.20613000 -0.33436800
H 1.15059400 -1.81839300 1.26559500
O -0.73322100 -1.10888000 -0.03446300
H -0.49570300 1.86977900 0.71847700
O 0.40822500 1.92683000 1.08868700

Sum of electronic and zero-point Energies= -619.383245

Number of Imaginary Frequencies= 2
Figure 4.5c.
C -1.55801100 -0.86827500 -0.01634100
O -2.12518300 0.17772100 -0.59183200
N 1.10723600 1.45677200 -0.74826800
H -0.14275900 2.44646300 0.36703300
N -2.75314600 -1.28669700 0.20188800
O 2.26529900 -0.99142700 0.85525700
Ni 1.07705900 -0.08490500 -0.33403100
H 1.64146200 -1.41536100 1.44591000
O -0.35094200 -1.19375100 0.18140300
H -1.52060900 1.80655600 0.47647100
O -0.94746300 2.45230400 0.92844100

Sum of electronic and zero-point Energies= -619.398179

Number of Imaginary Frequencies= 1
Figure 4.6a.
C -1.82804700 0.19467100 -0.00024900
O -2.23271100 -1.05845200 0.00616400
N 1.97273000 -1.44818500 -0.00202400
N -3.07606300 0.50789200 -0.00490500
O 1.81955400 1.48553400 0.00312700
Ni 0.94313600 -0.21151400 -0.00089600
H 1.04159700 2.04459100 0.00486400
O -0.68156600 0.73439600 -0.00051200
 79

Sum of electronic and zero-point Energies= -542.992980

Number of Imaginary Frequencies= 1

Figure 4.6b.
C -1.63484600 -0.09523300 -0.00410300
O -2.83955600 -0.37128000 0.01681500
N 1.11450600 1.52061700 0.62042600
N -1.06448400 0.94766600 -0.61927200
O 2.02456000 -1.19952400 -0.27830400
Ni 0.70852500 0.17304800 -0.09887300
H 1.65641400 -1.86311300 0.30640300
O -0.68952800 -0.89029800 0.57131000

Sum of electronic and zero-point Energies= -543.003947

Number of Imaginary Frequencies=2

Figure 4.6c.
C -1.77365400 -0.14105900 0.00890900
O -2.97989100 -0.30110800 0.03424500
N -0.00409200 1.34012200 -0.02902100
N -1.22717800 1.28134900 -0.01027800
O 2.76664500 0.03632900 -0.05209600
Ni 0.88179200 -0.27035900 -0.01508000
H 2.96961400 0.44625400 0.78964600
O -0.83662600 -1.03273900 -0.00037100

Sum of electronic and zero-point Energies= -543.202457

Number of Imaginary Frequencies= 1

Figure 4.7a.
C 1.20477200 -0.76897600 0.05966100
O 1.85529500 -1.68279900 0.64009700
N 0.30534900 0.14547400 1.01417700
H 0.67818100 1.11212400 1.01899500
H 0.26404500 -0.27581900 1.94032500
H 3.02345900 0.25160400 -0.15776700
N 2.11110400 0.28811100 -0.60411100
H 2.19992300 0.07273300 -1.59702100
O -2.99382400 0.53908400 0.05754000
Ni -1.21216700 -0.12352700 -0.12886100
H -3.44559700 -0.01897600 0.69175900
O 0.21439700 -1.07721100 -0.89684500
 80

H 1.03501000 2.35076700 -0.63881400

O 1.67936100 2.41406100 0.08948300

Sum of electronic and zero-point Energies= -621.290518

Number of Imaginary Frequencies= 1

Figure 4.7b.
C 1.11893100 -0.73269800 0.05283800
O 1.92178300 -1.43583100 0.82940900
N 0.31997700 0.37140100 0.75932000
H 0.79280000 1.35376400 0.57014000
H 0.29309100 0.14710300 1.75441800
H 2.20324600 1.06996200 -0.52331000
N 2.03676700 -0.02633800 -0.82170100
H 2.72240500 -0.64937200 -1.23704700
O -2.91919800 0.74401700 0.00072800
Ni -1.24860500 -0.17519500 -0.11003000
H -3.32197200 0.46847600 0.82511500
O 0.08690300 -1.41727000 -0.56617600
H 1.38512900 2.75363600 -0.67991600
O 1.86994300 2.32691200 0.04742200

Sum of electronic and zero-point Energies= -621.301259

Number of Imaginary Frequencies=2

Figure 4.7c.
C 0.99746100 -0.78442200 0.08853800
O 1.81397600 -1.49510900 0.90042200
N 0.38280100 0.42593500 0.66379300
H 1.45038100 1.81702300 0.39054500
H 0.30536100 0.23990700 1.66850400
H 2.56283500 0.41764900 -0.60344900
N 1.98359200 -0.35347000 -0.94270900
H 2.53471600 -1.14934600 -1.25722700
O -2.92928800 0.86073800 -0.05867100
Ni -1.28226400 -0.10614900 -0.08192800
H -3.35673400 0.65211500 0.77291200
O -0.05528100 -1.48195200 -0.45081800
H 1.82922200 2.65544200 -0.82412500
O 2.17410300 2.43365500 0.05506900

Sum of electronic and zero-point Energies= -621.317789

Number of Imaginary Frequencies= 1
 81

Figure 4.8a.
C 2.07533200 0.15923400 0.05206000
O 1.91428500 1.35279200 0.33248100
N -0.98069100 1.13176900 -0.60469600
H -0.19066600 1.64968800 -0.19527700
H 4.03864900 0.18640400 0.54568700
N 3.39767200 -0.35319800 -0.02314400
H 3.44676700 -1.34977100 0.15291500
O -2.52425600 -1.00716700 0.24593200
Ni -0.68445500 -0.59698500 -0.06226100
H -2.59765000 -0.95643800 1.19976900
O 1.18239400 -0.73350200 -0.23729300
O -2.09995500 1.63084400 0.16401700
H -2.68296300 0.83655000 0.08163100

Sum of electronic and zero-point Energies= -620.767669

Number of Imaginary Frequencies= 1

Figure 4.8b.

C -2.01971700 -0.04641800 0.03517700

O -1.63251600 1.14885200 0.05996500
N 1.44529700 -1.24220100 0.00133000
H 2.54472200 -0.97774800 0.60593200
H -3.96335600 0.38467800 -0.29700100
N -3.38071700 -0.36026500 0.06348300
H -3.58822800 -1.27189000 -0.32512200
O 1.52765100 1.48282000 -0.11058600
Ni 0.33632700 0.08971000 -0.03435800
H 1.48228400 1.85457200 0.78646500
O -1.18267700 -1.01696300 0.01359700
O 3.38207700 -0.53705400 -0.00544700
H 3.01739700 0.37303700 -0.13324000

Sum of electronic and zero-point Energies= -620.710005

Number of Imaginary Frequencies= 2

 82

Figure 4.8c.

C 1.92185800 0.18612900 -0.06240300

O 1.31353900 1.18693000 0.44695700
N -0.21271600 0.89510200 0.67233400
H -2.82797000 0.76435300 -0.40241700
H 3.73100600 1.00943800 0.30147100
N 3.28794200 0.33039700 -0.30551700
H 3.76579300 -0.56249900 -0.32411500
O -2.38315200 -0.94589000 0.14991600
Ni -0.49067200 -0.73092200 0.00705700
H -2.54290500 -0.87886600 1.09212100
O 1.34181800 -0.89563300 -0.37927400
O -2.72928200 1.73246700 -0.56262400
H -1.78824100 1.81513400 -0.29776600

Sum of electronic and zero-point Energies= -620.710005

Number of Imaginary Frequencies=1

Figure 4.9a.
C -1.10122000 0.39373100 -0.18453500
O -0.55989300 1.65287000 0.10855100
N 0.80418900 1.66410000 0.23462000
H -2.83943900 1.29120000 -0.18867400
N -2.40089700 0.38732100 -0.36498100
H -3.02709300 -0.40148200 -0.20352100
O 2.73944200 -1.48309000 -0.03380100
Ni 1.47603800 -0.05218100 0.03261500
H 3.62369500 -1.14916200 0.12225100
O -0.30589800 -0.58011800 -0.25090900
O -4.08180100 -1.23072900 0.24513900
H -3.63676600 -1.87328000 0.82461900

Sum of electronic and zero-point Energies= -620.078074

Number of Imaginary Frequencies=1

Figure 4.9b.
C 1.03551900 0.06890400 0.27798200
O 0.72848200 1.41223800 0.05818700
N -0.60113600 1.66506400 -0.15052500
H 3.09045600 0.40864900 0.15097200
N 2.29896700 -0.15961800 0.55800600
H 2.79023400 -1.05148900 0.28024500
O -2.99256100 -1.18496100 -0.07399000
 83

Ni -1.56030900 0.07859600 -0.08735300

H -2.61596100 -2.05287100 0.07657200
O 0.08957200 -0.76574800 0.22788900
O 4.34828800 -0.67666300 -0.56188500
H 4.93573800 -0.73543900 0.21621400

Sum of electronic and zero-point Energies= -620.068123

Number of Imaginary Frequencies=2

Figure 4.9c.
C 1.22622900 0.73729100 -0.00670100
O 0.32081600 1.80642100 0.01919000
N -1.02153600 1.44997900 0.00145100
H 2.63257000 1.99918400 0.03851600
N 2.49045500 0.98969800 0.00967500
H 3.42709400 -0.79707400 0.03125800
O -3.03500200 -0.86549300 -0.03561600
Ni -1.19376300 -0.35769400 -0.02680700
H -3.36695000 -0.65886100 0.83895700
O 0.68449700 -0.43699000 -0.04275500
O 3.36652200 -1.77574000 0.03426500
H 2.39816700 -1.85489400 0.00353100

Sum of electronic and zero-point Energies= -620.134964

Number of Imaginary Frequencies=1

Figure 4.10a.
C 1.28372000 0.36211600 -0.05855400
O 0.77513400 1.51590400 0.06553200
N -0.83279900 1.44016300 0.03944000
H 3.14490000 0.93437400 0.41503000
N 2.68242300 0.26792300 -0.19951600
O -3.12296400 -0.43741700 0.02286800
Ni -1.22047900 -0.28288700 -0.04619700
H -3.30299800 -0.25129400 0.94520700
O 0.60760900 -0.71283000 -0.13363700
O 3.15887000 -1.03249500 0.20545400
H 2.33261900 -1.55683400 0.12340100

Sum of electronic and zero-point Energies= -619.445090

Number of Imaginary Frequencies=1
 84

Figure 4.10b.
C 1.07048800 1.22872700 0.01385300
O 1.87619200 2.11851100 -0.23583100
N -2.82397300 -0.22638400 -0.41218900
H 2.15024300 -0.70207600 -0.07420300
N 1.50094800 0.00940000 0.53803600
O 0.37911500 -0.93155500 0.61282500
Ni -1.28692600 -0.17631400 0.06326300
H 0.81515100 -1.65751900 0.16492600
O -0.24553100 1.37622300 -0.13554800
O 2.14338100 -2.06472300 -0.60101200
H 2.68153000 -2.54474400 0.05039800

Sum of electronic and zero-point Energies= -619.418264

Number of Imaginary Frequencies=2

Figure 4.10c.
C -1.03104100 -0.61339600 0.02962100
O -2.01134700 -1.38501600 0.06616600
N 3.16613400 -0.32873800 0.14334800
H -3.62230600 -0.35434900 0.00499100
N -1.20226600 0.73400000 0.12515900
O 0.14225200 1.31385500 -0.06078000
Ni 1.63771900 0.12580200 -0.04638300
H 0.07969200 2.19215700 0.31662700
O 0.21561600 -1.10288000 -0.09498200
O -4.15372800 0.47130500 -0.03992200
H -3.41670700 1.10516200 -0.04402100

Sum of electronic and zero-point Energies= -619.431958

Number of Imaginary Frequencies= 1

Figure 4.11a.
C -1.43331000 -0.57440100 0.05632800
O -2.46176500 -1.22281500 -0.17251000
N -1.54662400 0.82412800 0.27775200
H -0.73200100 1.34066500 -0.04021800
H -3.22462500 0.72246100 -0.71904600
N -2.76397700 1.44029300 -0.14895600
H -3.35303500 1.49551600 0.68451700
O 3.06344400 0.79265900 -0.13256200
Ni 1.40847700 -0.15263700 -0.00766600
H 3.69522900 0.19496600 0.26915300
 85

O -0.23278600 -1.05538400 0.15266100

Sum of electronic and zero-point Energies= -544.993594

Number of Imaginary Frequencies= 1

Figure 4.11b.
C 1.67138600 -0.23508800 -0.01004800
O 2.85490100 -0.05748600 0.25548100
N 0.81855100 -1.23915400 0.45123400
H 0.95356300 -1.46292600 1.43577200
H -0.82075600 2.18524000 1.23917600
N -0.74859600 2.70981400 0.35181500
H 0.06312900 2.25077100 -0.09945700
O -2.45950900 -0.75164800 0.25640100
Ni -0.66286500 -0.28575000 -0.19427500
H -2.64313900 -1.55311300 -0.23522800
O 0.91578500 0.52125300 -0.81958300

Sum of electronic and zero-point Energies= -544.942875

Number of Imaginary Frequencies=2

Figure 4.11c.

C -1.32900000 0.05968900 -0.08359900

O -2.27563200 0.50500300 -0.95108900
N -0.33787300 1.04021700 0.35109000
H -0.28957900 1.73150100 -0.40713600
H -2.71759000 0.52720100 1.38973300
N -2.21435400 -0.30173600 1.07425000
H -2.88588400 -1.00297700 0.75874600
O 2.86966300 0.20088300 0.25633600
Ni 1.02069900 -0.17470700 -0.04092500
H 3.15880300 0.63677800 -0.54625900
O -0.59474800 -1.02191300 -0.49586800

Sum of electronic and zero-point Energies= -544.904115

Number of Imaginary Frequencies=1

Figure 4.12a.
C 1.20228000 -1.00064900 -0.14041600
O 2.34234600 -1.34082300 0.10842900
N 0.66153000 0.33815300 0.12692400
H 0.81933100 1.07303700 -0.56260100
 86

H 2.00659000 0.51053300 1.54305200

N 1.12199600 0.96965600 1.32602600
H 1.33025200 1.88828700 0.93468600
O -2.67560200 0.55203300 0.38811800
Ni -1.06992100 -0.38037800 -0.05965500
H -2.82520500 1.17051000 -0.32803000
O 0.18564800 -1.66911600 -0.60472400
O 1.21941500 2.45273900 -0.93044000
H 0.35400700 2.89877200 -0.93598600

Sum of electronic and zero-point Energies= -620.736065

Number of imaginary frequencies=1

Figure 4.12b.
C 0.88637500 1.22595500 -0.01745800
O 1.99165100 1.71551000 -0.00849800
N 0.59656000 -0.23096000 0.03473600
H 1.05761700 -0.74606800 -0.76922600
H 0.45076000 -1.62838200 1.39209800
N 1.14750600 -0.89842700 1.20609900
H 1.97771500 -1.51529200 0.48205000
O -2.54868000 -1.23192000 -0.00602000
Ni -1.23352100 0.15195500 -0.06386700
H -2.57693400 -1.61157200 -0.88512800
O -0.29129900 1.77796500 -0.11590400
O 2.46372800 -1.88274000 -0.65093700
H 3.17952500 -1.23396800 -0.76173300

Sum of electronic and zero-point Energies= -620.733923

Number of imaginary frequencies= 2

Figure 4.12c.
C 0.88245100 1.03228600 0.04788700
O 2.03898900 1.40571300 -0.02163800
N 0.47536800 -0.41708700 -0.00890200
H 0.75418100 -0.81002300 -0.91980100
H 0.51667900 -2.09565200 0.89504600
N 0.90114300 -1.16285800 1.09303700
H 2.61812300 -1.41212200 0.20598900
O -2.75976600 -1.09439300 -0.20277400
Ni -1.33230600 0.16404200 -0.03906800
H -2.92282100 -1.16293500 -1.14430400
O -0.22666400 1.67589400 0.12298000
O 3.22228400 -1.23539000 -0.55894600
 87

H 3.20939900 -0.26113200 -0.53627800

Sum of electronic and zero-point Energies= -620.745255

Number of Imaginary Frequencies= 1

Figure 4.13a.
C -1.05145600 0.82665700 -0.15465900
O -2.03201400 1.53156600 0.10256500
N -1.25927300 -0.51796800 -0.62364400
H -0.59857500 -1.14814600 -0.16008800
H -2.59701900 -1.90944500 -0.82555400
N -2.60321200 -0.92134600 -0.57442200
O 3.38847000 -0.84863400 0.09637700
Ni 1.73762200 0.11055000 0.04379800
H 3.13720800 -1.74107200 0.33759300
O 0.18726700 1.16947800 -0.05353100
O -3.05519400 -0.99596900 0.82535900
H -3.15712200 -0.03301700 0.96996400

Sum of electronic and zero-point Energies= -620.159263

Number of Imaginary Frequencies= 1

Figure 4.13b.
C 0.90139800 1.23664100 -0.02634000
O 1.75293600 2.09188700 -0.15191200
N 1.31962600 -0.11823100 0.43495000
H 0.56100200 -0.81719800 0.41730300
H 2.67775400 -1.46271800 0.74953700
N 2.52076000 -0.41539300 0.71600300
O -3.19803000 -1.19682900 0.09359400
Ni -1.71774300 -0.00042700 -0.06600200
H -2.80602100 -2.06904500 0.15131600
O -0.36915000 1.30236700 -0.20174300
O 3.22145900 -1.92062400 -0.58611700
H 4.11525200 -1.53795900 -0.59929400

Sum of electronic and zero-point Energies= -620.122504

Number of Imaginary Frequencies=2
 88

Figure 4.13c.
C 0.45338500 1.62193200 0.00034500
O 1.06372000 2.66592200 0.00334700
N 1.30628900 0.29921100 -0.00983600
H 0.64645600 -0.53745400 -0.01105300
H 3.43696500 -1.44664900 -0.01457500
N 2.51444900 0.23624500 -0.01471100
O -2.84091100 -1.81938300 -0.00510000
Ni -1.72880600 -0.26656300 0.00337600
H -2.23087000 -2.55803800 -0.00675700
O -0.79682800 1.36617000 0.00380000
O 4.09381200 -2.18429600 0.00245500
H 4.93020100 -1.70119900 0.07159100

Sum of electronic and zero-point Energies= -620.167276

Number of Imaginary Frequencies=1

Figure 4.14a.
C 1.87237300 -0.12034900 -0.06347700
O 3.10232700 -0.11537100 -0.06692000
N 1.15502300 1.10443100 -0.07318500
H 1.68057300 1.86216600 0.35722700
N -0.15046500 0.98959200 0.50297200
O -2.59182200 -0.31285700 0.01764400
Ni -0.71911900 -0.68791800 0.03788800
H -2.81104200 -0.31614500 -0.91493100
O 1.09370600 -1.17198500 -0.07935100
O -0.99680800 1.89219600 -0.25532200
H -1.85957300 1.44374200 -0.05923000

Sum of electronic and zero-point Energies= -619.562461

Number of Imaginary Frequencies=1

Figure 4.14b.
C 1.47486200 -0.66919400 0.06258000
O 2.58927600 -1.11176000 0.23345300
N 1.07900000 0.61611900 0.72037600
H 1.82346400 1.17489400 1.13909100
N -0.13958400 0.87589900 0.94022500
O -2.98581800 0.26133800 -0.00660300
Ni -1.14870600 -0.25355200 -0.09609000
H -3.04988400 1.07419400 -0.50951900
O 0.43474400 -1.18296600 -0.50016200
 89

O 2.05541500 1.58250900 -0.83761800

H 1.21617500 2.02845200 -1.05129600

Sum of electronic and zero-point Energies= -619.519978

Number of Imaginary Frequencies=2

Figure 4.14c.
C -0.97219500 -1.46887400 0.01016600
O -1.86348000 -2.29451100 0.04041400
N -1.34638900 0.00638600 -0.01146900
H -2.89407200 1.46493500 0.01137300
N -0.38306600 0.76807900 -0.03326900
O 2.62666500 1.30733700 -0.04417700
Ni 1.26491900 -0.03170300 -0.01733200
H 2.57281700 1.74824200 0.80462600
O 0.30860600 -1.65025500 -0.00497000
O -2.96390500 2.43822500 0.00474700
H -2.02021400 2.66010900 -0.04664700

Sum of electronic and zero-point Energies= -619.603755

Number of Imaginary Frequencies=1
Figure 4.15a.
C 1.85361000 -0.69527000 0.00091400
O 2.69658600 -1.58546300 0.05749100
N -2.19381500 -0.69743100 -0.01696000
N -3.03606200 -1.43428000 0.02505900
O 0.06399500 2.18771100 -0.03204300
Ni -0.74856200 0.45923400 -0.01727400
H 0.13435100 2.48004500 0.87754700
O 0.55852900 -0.89189500 0.00180700
O 2.28225800 0.60559500 -0.07008500
H 1.50191500 1.22742000 -0.11339900

Sum of electronic and zero-point Energies= -619.102835

Number of Imaginary Frequencies= 1

Figure 4.15b.
C 2.07737000 -0.45788100 0.01378600
O 3.08608700 -1.14307300 0.13593200
N -2.37830500 -0.55203600 0.09565100
N -3.43377200 -0.92670700 0.19530400
O -0.33935300 1.97861600 -0.12792400
Ni -0.68252400 0.10037600 -0.07744500
 90

H -0.53759300 2.38683300 0.71577200

O 0.88501100 -0.91719300 -0.28187000
O 2.18771100 0.90001700 0.18733400
H 1.31294000 1.35420300 0.02549500

Sum of electronic and zero-point Energies= -619.096785

Number of Imaginary Frequencies=2

Figure 4.15c.
C -1.51305700 -0.99905100 0.02089600
O -2.61158000 -1.40528200 -0.32088400
N -1.01175700 2.42502400 0.37036200
N -1.48718000 2.67041300 -0.59690900
O 3.02054600 0.28074300 0.22431900
Ni 1.25514200 -0.32156200 -0.18638400
H 2.99958700 0.47718500 1.16172800
O -0.44890900 -0.90362500 -0.72657900
O -1.35425600 -0.57776200 1.33634100
H -0.41907400 -0.29979600 1.41190700

Sum of electronic and zero-point Energies= -619.094919

Number of Imaginary Frequencies= 1

Figure 4.16a.
C 1.95169500 -0.14060800 0.04005900
O 3.05976200 -0.64582300 0.15361100
O -2.76653900 -0.39470300 0.34836600
Ni -0.90896200 -0.30726900 -0.08737100
H -2.77721800 -0.26993600 1.29814700
O 0.88502900 -0.78408700 -0.38509100
O 1.77194400 1.17261900 0.35679900
H 0.83480500 1.43149500 0.15065600
O -0.78521400 1.46528700 -0.37543900
H -1.63667100 1.77926800 -0.02875300

Sum of electronic and zero-point Energies= -585.380718

Number of Imaginary Frequencies=1

Figure 4.16b.
C 1.79641700 -0.00963800 0.13052900
O 3.01358100 -0.19572800 0.16389200
O -2.54966500 -0.23536600 0.55097800
Ni -0.76634400 -0.42748000 -0.10549700
 91

H -2.45825200 -0.21433500 1.50437500

O 1.00250900 -0.83668200 -0.59346600
O 1.14975300 0.94479900 0.76174000
H 0.06349600 1.51776400 -0.14201400
O -0.78610100 1.45640600 -0.75672100
H -1.56673800 1.65641300 -0.20300100

Sum of electronic and zero-point Energies= -585.354161

Number of Imaginary Frequencies=2

Figure 4.16c.
C 1.74801200 0.34345300 0.03470600
O 2.80315800 0.94982800 0.08126800
O -2.19391200 -0.81692000 0.14615900
Ni -0.29431100 -0.72541800 -0.03060100
H -2.38395800 -0.87326100 1.08342800
O 1.54657900 -0.90880200 -0.36510600
O 0.54518500 0.83864600 0.39620700
H -1.26952200 1.99212100 -0.10830200
O -2.22596700 1.95512400 -0.27659400
H -2.39422600 0.98911600 -0.18200300

Sum of electronic and zero-point Energies= -585.389147

Number of Imaginary Frequencies= 1

Figure 4.17a.
C -1.57006600 -0.05627200 0.00681100
O -2.78384100 -0.18973200 0.02369600
O 2.60967800 -0.20197200 -0.07037200
Ni 0.72906000 0.12738300 -0.01651300
H 2.87080600 -0.37518500 0.83493100
O -0.88717500 1.08717500 0.01487600
O -0.67167200 -1.05221100 -0.01987800

Sum of electronic and zero-point Energies= -508.978193

Number of Imaginary Frequencies=1
 92

Figure 4.17b.
C -1.83991200 0.00009500 0.02852300
O -2.40824700 -1.06644000 -0.32254400
O 2.84993300 0.00044600 -0.50413500
Ni 1.03944500 -0.00029500 0.10433300
H 3.50864600 0.00181000 0.19146500
O -0.73053400 -0.00034400 0.73803200
O -2.40785800 1.06707400 -0.32184500

Sum of electronic and zero-point Energies= -508.809218

Number of Imaginary Frequencies=2

Figure 4.17c.
C -2.08348900 -0.53288100 0.00291700
O -3.18104700 -0.15537300 -0.01856600
O 2.30042100 -1.06685600 -0.01230200
Ni 0.95452600 0.28833100 -0.00066100
H 1.93702600 -1.95309600 0.00460900
O -0.16030000 1.80210800 0.00571400
O -0.97942600 -0.94523900 0.02470100

Sum of electronic and zero-point Energies= -508.806195

Number of Imaginary Frequencies=1
 93

APPENDIX B:

SUPPORTING INFORMATION FOR CHEMICAL OXIDATION OF UREA

Figure 5.1a.

Cartesian Co-ordinates

C 1.79999000 -0.27177200 0.01907400

O 2.47628600 -1.24210400 -0.24614600
N 1.99579300 1.02149400 -0.29783000
H 1.17481100 1.64682200 -0.26584000
H 2.76085800 1.22065900 -0.92750300
H 0.51542400 -1.43418000 1.09125100
N 0.57107600 -0.44743500 0.83845100
H 0.62807100 0.11146100 1.69279800
O -2.00042900 -1.32354100 -0.34514300
Ni -1.10904300 0.16156700 -0.01248300
H -1.53119700 -2.12569400 -0.61949500
O -0.63370500 1.77430300 0.02623100

Sum of electronic and zero-point Energies= -545.478109

Number of Imaginary Frequencies= 0

Figure 5.1b.
C -1.79914400 -0.20186200 -0.00811300
O -0.69068500 -0.79472300 0.08449100
N -2.94461500 -0.93478100 0.13396200
H -3.80994000 -0.58804200 -0.25565400
H -2.81538600 -1.93683600 0.10789800
H -1.01264300 1.64306800 -0.16896100
N -1.90334600 1.12072100 -0.23359600
H -2.77604700 1.60150300 -0.07094700
O 2.59110700 -0.93860000 -0.17292700
Ni 1.11318100 0.02580200 -0.02517600
H 3.02872500 -1.16549900 0.66263400
O 0.71793200 1.68744200 0.23544500

Sum of electronic and zero point Energies= -545.482146

Number of Imaginary Frequencies= 0

 94

Figure 5.1c.
C 1.87733800 0.03577100 -0.01829500
O 3.05747600 -0.11991500 0.17401700
N -2.18224100 -1.08778200 0.05514600
H -2.27774300 -1.68407000 0.87698900
H -2.33964100 -1.65468600 -0.77825000
H 1.30893300 1.98016200 -0.02933900
N 1.00353700 1.02227400 -0.13759700
H -2.87274100 -0.33059300 0.09564000
O 0.98987200 -1.15452300 -0.17801600
Ni -0.60526100 0.09471300 -0.01894200
H 1.33476600 -1.86541000 0.38892400
O -1.69976800 1.41775900 0.08691800

Sum of electronic and zero-point Energies= -545.492283

Number of Imaginary Frequencies= 0

Figure 5.1d.
C 1.41709000 -0.01699400 0.08075200
O 1.83677600 -0.71645200 1.13680100
N 0.39217400 1.04688300 0.49994200
H 0.52026600 1.94794500 0.03881700
H 0.42578200 1.17902500 1.51094400
H 3.22910400 -0.08598300 -0.75036700
N 2.47127100 0.58917500 -0.67591300
H 2.15179700 0.80659800 -1.61984000
O -2.75475400 0.19854100 0.01374500
Ni -1.03883900 -0.13894400 -0.13879000
H -3.16555000 0.21392000 0.89076100
O 0.59040700 -0.92227900 -0.58015900

Sum of electronic and zero-point energies=

Number of Imaginary Frequencies= 0

 95

Figure 5.1e.

C 1.71291800 -0.44840700 0.01029800

O 2.62526100 -1.11562200 -0.45310900
N 1.94385400 0.94163000 0.38932100
H 0.60634200 1.72396200 -0.12224000
H 1.81155000 1.05630900 1.39489600
H 0.33158300 -1.84568400 0.04647300
N 0.44408500 -0.85921000 0.26100300
H 2.90604400 1.17816700 0.15586200
O -0.40794400 1.85223100 -0.22389400
Ni -1.15224800 0.05584300 -0.00267500
H -0.58575300 2.25804500 -1.08795400
O -2.19230600 -1.21422200 0.06122900

Sum of electronic and zero-point Energies= -545.473262

Number of Imaginary Frequencies= 0

Figure 5.2a.
C -1.82316000 -0.24239000 0.01975200
O -2.55328600 -1.13695200 -0.35074500
N -1.97383000 1.09072400 -0.14353600
H -1.12406800 1.67220000 -0.09544600
H -2.72889600 1.37104700 -0.75445700
H -0.59547900 -1.56764400 0.95055800
N -0.60348500 -0.56182000 0.78547000
H -0.59210900 -0.06419400 1.67783600
O 0.67900800 1.75585200 0.08121300
Ni 1.16539200 0.02173500 -0.05718900
H 1.30277400 2.39748300 -0.28939300
O 1.88514900 -1.45208300 -0.29295200

Sum of electronic and zero-point Energies= -545.482798

Number of Imaginary Frequencies= 0

 96

Figure 5.2b

C 1.41709000 -0.01699400 0.08075200

O 1.83677600 -0.71645200 1.13680100
N 0.39217400 1.04688300 0.49994200
H 0.52026600 1.94794500 0.03881700
H 0.42578200 1.17902500 1.51094400
H 3.22910400 -0.08598300 -0.75036700
N 2.47127100 0.58917500 -0.67591300
H 2.15179700 0.80659800 -1.61984000
O -2.75475400 0.19854100 0.01374500
Ni -1.03883900 -0.13894400 -0.13879000
H -3.16555000 0.21392000 0.89076100
O 0.59040700 -0.92227900 -0.58015900

Sum of electronic and zero-point Energies= -545.458736

Number of Imaginary Frequencies= 0

Figure 5.2c
C 1.80583200 -0.10139700 -0.02411800
O 2.99247700 -0.25106700 0.13320400
N 1.06771100 1.07737400 -0.19009400
H -1.99019300 -1.86640800 -0.80621600
H 1.29348200 1.78728400 0.50805800
H -1.88257900 -1.93002200 0.83565300
N -1.98112700 -1.29915900 0.04096500
H -2.86411400 -0.79402500 0.11557100
O -1.75674700 1.34830200 0.06994200
Ni -0.51757500 0.09400300 -0.01451300
H -1.35873700 2.22838400 -0.03206100
O 0.87091400 -1.08428800 -0.08139800

Sum of electronic and zero-point Energies= -545.538248

Number of Imaginary Frequencies= 0

 97

Figure 5.3a
C 1.42994700 -0.20637300 0.15512900
O 2.22621200 -0.80468300 0.86427400
N 0.26590400 0.76317100 0.77391800
H 0.93513500 1.55074100 0.02319100
H 0.13619100 0.70011700 1.78818100
H 2.90432300 1.27488800 -0.40529800
N 1.94848300 1.05870700 -0.68477700
H 1.88734900 0.93076800 -1.69438200
O -2.61170700 0.30015600 0.21530900
Ni -1.00679800 -0.21065100 -0.17878900
H -2.75577800 1.02453200 0.84312400
O 0.51083600 -0.88269000 -0.71752000

Sum of electronic and zero-point Energies= -545.458333

Number of Imaginary Frequencies= 1

Figure 5.3b

C 1.42994700 -0.20637300 0.15512900

O 2.22621200 -0.80468300 0.86427400
N 0.26590400 0.76317100 0.77391800
H 0.93513500 1.55074100 0.02319100
H 0.13619100 0.70011700 1.78818100
H 2.90432300 1.27488800 -0.40529800
N 1.94848300 1.05870700 -0.68477700
H 1.88734900 0.93076800 -1.69438200
O -2.61170700 0.30015600 0.21530900
Ni -1.00679800 -0.21065100 -0.17878900
H -2.75577800 1.02453200 0.84312400
O 0.51083600 -0.88269000 -0.71752000

Sum of electronic and zero-point Energies= -545.419332

Number of Imaginary Frequencies= 1

 98

Figure 5.5

Ni -0.05202400 -0.25123300 -0.00064900

O 1.75106900 -0.44884600 0.00038900
H 2.08459300 0.46194700 0.00616200
O -1.69139300 -0.50479200 0.00123000
O -0.01596700 1.56139300 -0.00045500
H -0.97759800 1.71055100 0.00271200

Sum of electronic and zero-point Energies= -396.138570

Sum of Imaginary frequencies= 0

Figure 5.6a.

Ni 0.90498000 -0.06165300 0.07464000

O 0.39570700 1.73806900 0.28008400
H 1.09816700 2.19952300 -0.20057000
O 1.27548100 -1.74192400 -0.00175800
O 2.53639900 0.39394300 -0.55680600
H 2.85236700 -0.51901000 -0.68349500
H -0.81141500 -1.60335800 0.72194200
N -0.96630800 -0.59524000 0.74210900
C -2.08702600 -0.16361900 -0.05256800
H -0.96213900 -0.20557000 1.68171900
O -2.83660300 -0.96115600 -0.60019600
N -2.16520100 1.19565200 -0.09250800

H -1.22145600 1.67176100 -0.02410500

H -2.82010200 1.53032900 -0.78781200

Sum of electronic and zero-point Energies= -621.369304

Number of Imaginary Frequencies=0
 99

Figure 5.6b.
Ni 0.92295100 -0.03617000 0.00837800
O 1.39352400 -1.76795800 -0.02652200
H 2.36208900 -1.67892600 -0.04308500
O 0.53345700 1.69433000 0.00480500
O 2.70598700 0.38481100 0.00399100
H 2.64403800 1.35359800 -0.01291100
H -0.45139900 1.74977300 -0.00781700
N -0.91081200 -0.63003800 0.03209900
C -2.06835900 0.02977300 -0.01341700
H -0.95967000 -1.63836300 -0.06357300
O -2.21020700 1.27173100 -0.01610800
N -3.25590600 -0.76759000 -0.09154100
H -3.19725600 -1.62560900 0.44898100
H -4.04533000 -0.20627500 0.21107900

Sum of electronic and zero-point Energies= -621.403613

Number of Imaginary Frequencies= 0

Figure 5.6c.
Ni 0.92295100 -0.03617000 0.00837800
O 1.39352400 -1.76795800 -0.02652200
H 2.36208900 -1.67892600 -0.04308500
O 0.53345700 1.69433000 0.00480500
O 2.70598700 0.38481100 0.00399100
H 2.64403800 1.35359800 -0.01291100
H -0.45139900 1.74977300 -0.00781700
N -0.91081200 -0.63003800 0.03209900
C -2.06835900 0.02977300 -0.01341700
H -0.95967000 -1.63836300 -0.06357300
O -2.21020700 1.27173100 -0.01610800
N -3.25590600 -0.76759000 -0.09154100
H -3.19725600 -1.62560900 0.44898100
H -4.04533000 -0.20627500 0.21107900

Sum of electronic and zero-point Energies= -621.403613

Number of imaginary frequencies= 0

 100

Figure 5.7a
Ni 0.83634700 -0.07634100 0.11034500
O 0.60221200 1.68834200 0.44563300
H 1.45141100 2.02002800 0.10458000
O 1.08594600 -1.80350200 -0.25112100
O 2.53840800 0.34014500 -0.48601700
H 2.85374500 -0.52784100 -0.78337000
H 0.22323800 -2.14191100 0.05900000
N -0.95152800 -0.56450300 0.74511300
C -2.05826300 -0.07983900 -0.01519700
H -0.99293300 -0.11575600 1.66394400
O -3.07267200 -0.74841000 -0.21582500
N -1.92630000 1.18710800 -0.52384700
H -1.05107600 1.69437000 -0.37504200
H -2.63888500 1.51686500 -1.15781800

Sum of electronic and zero-point Energies= -621.387529

Number of Imaginary Frequencies= 1

Figure 5.7b.

Ni -0.93043700 -0.06461400 -0.00014300

O -1.26439500 -1.81582100 0.00026000
H -2.23848300 -1.79526700 0.00061900
O -0.73286400 1.71621700 -0.00039500
O -2.74834800 0.19486200 0.00034600
H -2.77467400 1.16558100 0.00031100
H 0.21258900 1.94261500 -0.00036300
N 0.98126500 -0.45667800 -0.00037500
C 1.91307700 0.40346300 0.00013700
H 1.88717500 -1.35368000 -0.00058600
O 2.34208300 1.52997900 0.00060400
N 3.18627700 -1.12884200 -0.00011100
H 3.77160800 -1.23666800 -0.82965500
H 3.77095200 -1.23743100 0.82973600

Sum of electronic and zero-point Energies= -621.318147

Number of imaginary frequencies= 1