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20 mit icle b rt u S A Applied Mechanics r International Journal of Electro Mechanics and u Mechanical Behaviour International Journal of Machine Design and Yo Manufacturing

Mechanical Engineering

¬ International Journal of Thermal Energy and

¬ International Journal of Production Engineering ¬ International Journal of Industrial Engineering

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Applications

International Journal of Mechanical Dynamics and Analysis International Journal of Fracture and damage Mechanics International Journal of Structural Mechanics and Finite Elements

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Chemical Engineering « International Journal of Renewable Energy and its

Commercialization « International Journal of Environmental Chemistry « International Journal of Agrochemistry « International Journal of Prevention and Control of Industrial

Pollution

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Architecture « International Journal of Housing and Human Settlement

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International Journal of Water Resources Engineering International Journal of Concrete Technology International Journal of Structural Engineering and Analysis International Journal of Construction Engineering and Planning

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International Journal of Immunological Nursing International Journal of Cardiovascular Nursing International Journal of Neurological Nursing International Journal of Orthopedic Nursing International Journal of Oncological Nursing

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International Journal of Energetic Materials International Journal of Bionics and Bio-Materials International Journal of Ceramics and Ceramic Technology International Journal of Bio-Materials and Biomedical Engineering 4 more...

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International Journal of Thermodynamics and Chemical Kinetics International Journal of Thermodynamics and Chemical Kinetics welcomes research papers and review articles concerning the development in the field of thermodynamics and chemical kinetics. Maximum entropy thermodynamics, non-equilibrium thermodynamics, reaction's mechanism, gas phase kinetics and solution kinetics are a few topics that are included in the journal.

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Atmospheric thermodynamics

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EDITORIAL BOARD MEMBERS Dr. Chang-Yu Sun State Key Laboratory of Heavy Oil Processing China University of Petroleum Beijing, China

Dr. Rekha Lagarkha Asst. Prof. Department of Chemistry Bundelkhand University India

Prof. Karipeddi Ramakrishna Department of Chemistry, GIS GITAM University, Visakhapatnam, India

Dr. Vidyavati A. Shastry Professor and Head, Department of Chemistry SEA College of Engineering and Technology, K. R. Puram Bangalore, India

Dr. Yee-Wen Yen Professor/Vice Dean of College of Engineering Department of Materials Science and Engineering National Taiwan University of Science and Technology, Taiwan

Dr. Bharat Modhera Department of Chemical Engineering, Maulana Azad National Institute of Technology, Bhopal, India

Dr. Rose Philo Department of Chemistry, St.Paul's College, Kalamassery, Kochi, Kerala, India

Dr. Rajneesh Dutt Kaushik Department of Chemistry, Gurukul Kangri University, Haridwar (Uttarakhand), India

Dr. Sushil Kumar Chemical Engineering Department, Motilal Nehru National Institute of Technology (MNNIT), Allahabad, U. P., India

Dr. Niki Sweta Jha National Institute of Technology (NIT) Patna, Bihar, India

Dr. Ajaya Kumar Singh Department of Chemistry (DST-FIST Sponsored) Govt. V. Y. T. PG. Autonomous College, Chhattisgarh, India

Dr. Vidyavathi A. Shastry Department of Chemistry, SEA College of Engineering & Technology, K. R. Puram, Bangalore, India

Dr. Sandeep Rai Department of Chemistry/Polymer and Rubber, Shroff S.R. Rotary Institute of Chemical Technology, Vataria, Ankleshwar, India

Dr. Kishore Dasari Navin Fluorine International Limited, India

Dr. Lubna Najam Science Academy Coaching Centre, Mumbai

Ramakrishna Rao Department of Chemistry, GITAM School of Technology, GITAM University, Bangalore, Karnataka, India

Dr. Rajesh Kumar Sahu Department of Chemistry, Vishwavidyalaya Engineering College, Lakhanpur Sarguja University Ambikapur, Chattisgarh, India

Shaista Ali Department of Chemistry, GC University, Lahore, Punjab, India

EDITORIAL BOARD MEMBERS Ranganathan Subramanian Department of Chemistry, Indian Institute of Technology, Patna, Bihar, India

Dr. Annapurna Nowduri Department of Engineering Chemistry, A. U. College of Engineering (Autonomous), Andhra University,Visakhapatnam, Andhra Pradesh, India

Dr. Vajjiravel Murugesan Department of Chemistry, B. S. Abdur Rahman University, Chennai, Tamil Nadu, India

Dr. G Vijaya Lakshmi Department of Chemistry, University College of Technology, Osmania University, Hyderabad, Andhra Pradesh, India

Dr. A. K. Sood Department of Chemistry, Guru Nanak Dev University, Amritsar, Punjab, India

Dr. Suranani Srinath Department of Chemical Engineering, National Institute of Technology, Warangal, Andhra Pradesh, India

From the Editor's Desk Dear Readers, We would like to present, with great pleasure, the inaugural volume of a new scholarly journal, International Journal of Thermodynamics and Chemical Kinetics. This journal is part of the Applied Sciences, and is devoted to the scope of present Thermodynamics and Chemical Kinetics issues, from theoretical aspects to application-dependent studies and the validation of emerging technologies. This new journal was planned and established to represent the growing needs of Thermodynamics and Chemical Kinetics as an emerging and increasingly vital field, now widely recognized as an integral part of scientific and technical investigations. Its mission is to become a voice of Thermodynamics and Chemical Kinetics, addressing researchers and practitioners in this area. The core vision of International Journal of Thermodynamics and Chemical Kinetics in JournalsPub is to propagate novel awareness and know-how for the profit of mankind ranging from the academic and professional research societies to industry practitioners in a range of topics in Thermodynamics and Chemical Kinetics in general. JournalsPub acts as a pathfinder for the scientific community to publish their papers at excellently, well-timed & successfully. International Journal of Thermodynamics and Chemical Kinetics focuses on original high-quality research in the realm of Atmospheric, Biological & Chemical thermodynamics, Equilibrium thermodynamics, Reaction's mechanism, Gas phase kinetics, Solution kinetics etc. The Journal is intended as a forum for practitioners and researchers to share the techniques of Thermodynamics and Chemical Kinetics and solutions in the area. Many scientists and researchers have contributed to the creation and the success of Thermodynamics and Chemical Kinetics. We are very thankful to everybody within that community who supported the idea of creating an innovative platform. We are certain that this issue will be followed by many others, reporting new developments in the field of Thermodynamics and Chemical Kinetics. This issue would not have been possible without the great support of the Editorial Board members, and we would like to express our sincere thanks to all of them. We would also like to express our gratitude to the editorial staff of JournalsPub, who supported us at every stage of the project. It is our hope that this fine collection of articles will be a valuable resource for Thermodynamics and Chemical Kinetics readers and will stimulate further research into the vibrant area of Thermodynamics and Chemical Kinetics. Puneet Mehrotra Managing Director

Contents 1. The Decomposition of Tris-(Oxalato)-Manganate (III) Complex Ion as the Reaction Suitable for the Laboratory Practice on Chemical Kinetics Pavel Anatolyevich Nikolaychuk, Mariya Mikhaylovna Vayner

2. Kinetics and Mechanisms of the Reduction of Some Carbonyl Compounds with Sodium Dithionite in Aqueous Alkaline Medium P.O. Ukoha, F.N. Okafor

3. Kinetic and Mechanistic Study of Oxidation of Benzydamine Hydrochloride by Permanganate (VII) in Acidic Medium V. Shastry, B.C. Sateesh, S. Shashidhar, T.N. Padmini, K.S. Ravindra

4. A Note on: Thermodynamics in Our Daily Life Zeanut Akoijam

5. Chemical Composition in Atmosphere: An Introductory Approach for Students Amit Agnihotri

International Journal of Thermodynamics and Chemical Kinetics Vol. 2: Issue 2

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The Decomposition of Tris-(Oxalato)-Manganate (III) Complex Ion as the Reaction Suitable for the Laboratory Practice on Chemical Kinetics Pavel Anatolyevich Nikolaychuk*, Mariya Mikhaylovna Vayner Kafedra Analitičeskoj i Fizičeskoj Himii, Čelâbinskij Gosudarstvennyj Universitet, Brat'ev Kaširinyh, Chelyabinsk, Russian Federation

ABSTRACT The complex ion [Mn(C2O4 )3 ]3 is very photosensitive and rapidly decomposes at the daylight even at ambient temperatures. Although the mechanism of this reaction is complicated, its kinetic equation obeys the pseudo-first order. In addition, the tris-(oxalate)manganate ion has a low thermal stability, and the reaction of its decomposition is highly affected by temperature. This makes this reaction very suitable for demonstrating the laws of chemical kinetics to the students – both the first-order reaction kinetics and the dependency of the rate constant on temperature. The kinetic studies of this reaction using a photocolourimetric method were performed; the influence of the initial concentrations of the reagents and temperature on the rate was studied. The didactic implementation of the reaction was discussed. The methodical instruction for the organization of the laboratory practice is provided. Keywords: activation energy, Arrhenius equation, chemical kinetics, decomposition, firstorder reaction

INTRODUCTION Complex compounds of manganese (III) with various ligands have a very high chemical reactivity. The redox chemistry of Mn+3 is very diverse and was studied thoroughly.[1–4] One of such species of

interest is the complex of tervalent manganese with oxalate-ion. A tris(oxalate)-manganate (III) complex ion is formed in a solution according to the reaction[5,6]:

(1) or in ionic form:

(2)

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International Journal of Thermodynamics and Chemical Kinetics Vol. 2: Issue 2

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Kinetics and Mechanisms of the Reduction of Some Carbonyl Compounds with Sodium Dithionite in Aqueous Alkaline Medium P.O. Ukoha, F.N. Okafor* Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, Enugu State, Nigeria

ABSTRACT Kinetics of the reduction of some carbonyl compounds (acetophenone, benzophenone, benzaldehyde, and salicylaldehyde) with sodium dithionite was studied at 28± 0.5oC and basic concentration in the range of 0.01 to 0.05 mol dm-3 (NaHCO3). Under these conditions, the reaction rates were found to be first order with respect to sodium dithionite as plot of log kobs versus log [S2O42-] showed linearity to about 95% extent of reaction, however, the overall reaction rate was second order at constant [OH-]. Furthermore, order of reactions with respect to acetophenone, benzophenone, salicylaldehyde, and benzaldehyde was unity as the plot of log(A∞-At) versus time showed about 90% linearity. Reaction rates increased with ionic strength and addition of chloride ions of varying concentration. Michaelis–Menten plot of 1/kobs versus 1/[S2O42-] were linear and have small intercepts on y-axis. Increase in pH (from 1-13) also showed remarkable increase in the reaction rates. Kinetic investigations showed that an outer-sphere reaction mechanism was operational and plausible mechanisms have been proposed for these reactions. The rate laws for the reactions conform to the equations: Rate = {k3K1 + k2 [OH-] 2} [S2O42-] [RCHO] where RCHO = benzaldehyde and salicylaldehyde Rate = {k3K1 + k2 [OH-] 2} [S2O42-] [RCOR1] where RCOR1 = benzophenone and acetophenone Keywords: carbonyl compounds, dithionite ions, kinetics, mechanism, reduction

INTRODUCTION Over the years, a lot of interests have been devoted to the study of redox reactions using sodium dithionite[1–3] due to its strong reducing ability, the kinetic study of these redox processes have also been shown[4] but not to a large extent. Dithionite ion is used to reduce carbonyls to their corresponding alcohols,[5] and the reduction, monitored kinetically.[6] It is a white crystalline powder with a weak sulfurous odor,[7] readily available inexpensive reducing agent that is capable of reducing a variety of functional groups e.g. nitro, nitroso, oximes, aldehydes,

ketones, diazonium salts, imines and haloketones.[8] Its reducing power is known to be generally enhanced in basic pH.[9] Though stable under most conditions, it gets decomposed in hot water and acidic solutions.[10] It produces sulphonyl anion, SO2- by reversible dissociation; (1) This anion is a stronger reducing agent than S2O42- as shown by its redox potential.[11] Redox reactions of dithionite

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International Journal of Thermodynamics and Chemical Kinetics Vol. 2: Issue 2

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Kinetic and Mechanistic Study of Oxidation of Benzydamine Hydrochloride by Permanganate (VII) in Acidic Medium V. Shastry1*, B.C. Sateesh2, S. Shashidhar1, T.N. Padmini3, K.S. Ravindra1 1

Department of Chemistry, South East Asian College of Engineering & Technology, Bangalore, India 2 Department of Chemistry, Shri Pillappa College of Engineering, Bangalore, India 3 Department of Chemistry, Shri Krishna Institute of Technology, Bangalore, India

ABSTRACT The kinetics and mechanism of Permanganate (Mn (VII)) oxidation of Benzydamine hydrochloride (B.HCl) in acidic medium has been studied at 26 ± 0.1°C. The reaction shows first order dependence in [Mn (VII)], less than unit order in [B.HCl] and fractional order dependence in [H2SO4]. Variation of ionic strength by the addition of KCl has no significant effect on the rate. The stoichiometry of the reaction is found to be 1:4 and the main oxidative products were toluene, dimethyl aza propionic acid and benzoic acid. A mechanism involving formation of complex has been proposed and the reaction constants involved in the different steps of mechanism are calculated. Activation parameters with respect to slow step of the mechanism are calculated and tabulated. The rate constant of reaction is found to be 1.960 × 10−3 s-1. Keywords: benzydamine hydrochloride, oxidation, potassium permanganate

INTRODUCTION The nonsteroidal anti-inflammatory drug, Benzydamine hydrochloride (B.HCl) shows local anaesthetic and analgesic action by stabilizing the cellular membrane and inhibiting prostaglandin synthesis.[1] Benzydamine hydrochloride has a tendency of increasing therapeutic effect; hence it is used as an adjunct to other therapy. It is also used in the treatment of Strains, Bursitis, Sprains, Synovitis, Myalgice, Tendinitis and Periathritis (musculoskeletal disorders).[2] Benzydamine shows prominent invitro antibacterial activity and also shows synergic property in combination with many antibiotics especially tetracyclines, against antibiotic resistance strains of

Staphylococcus aureas and Pseudomonas aeruginosa (Figure 1).[3,4] N N

CH3 CH3

Fig. 1. Structure of benzydamine. In general anti-inflammatory drugs are organic acids but benzydamine is a base and available as its hydrochloride salt. Benzydamine is fluorescent (exeitation 306nm: emission 362nm) and is detected fluorometrically in HPLC assay. In over dosage it acts as deliriant and CNS stimulant.[5] Potassium permanganate [Mn (VII)] will oxidize a wide variety of inorganic and

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International Journal of Thermodynamics and Chemical Kinetics Vol. 2: Issue 2

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A Note on: Thermodynamics in Our Daily Life Zeanut Akoijam* Department of Chemistry, Manipur University, Manipur, India

ABSTRACT Thermodynamics plays crucial role in our day-to-day life. Almost all the activities that we do or observe are all based on the principles of thermodynamics. Here, some of the common routine activities are brought into limelight that is explained by the phenomenon of thermodynamics. Keywords: energy, entropy, heat transfer, thermodynamics

BACKGROUND Thermodynamics is the field of science that deals with relationships between heat, work and energy. The term thermodynamics is actually a combination of two words viz., thermo (meaning thermal energy or heat) + dynamics (meaning study of forces or motion). This field of science involves various cyclic transformations between heat and energy. Because of this, some define thermodynamics as the study of energy and its various interconversions from one to another form [1]. It is applicable to various scientific fields including physics, biology and chemistry. Scientists argue that everything that occurs in our day-today activities like the driving of vehicles (cars, motorbikes, airplanes, ships), jetengines, spark-ignition engines etc., is entirely because of thermodynamics. The study of thermodynamics is based on different laws: first law of thermodynamics, second law of thermodynamics and third law of thermodynamics. Also, there is the zeroth law of thermodynamics, Boyle’s law, Charles law etc., which explains numerous activities occurring in nature. The first law of thermodynamics states that the total energy always remains conserved. It

means that the energy can neither be created nor destroyed but can only be converted from one form to another [2, 3]. The second law is the law of entropy. According to this, systems always try to maintain their state of thermodynamic equilibrium. Also, referred as the state of maximum entropy, second law of thermodynamics describes that the heat energy flows from a state of low temperature to a state of higher temperature. The topic of entropy is further extended to the third law of thermodynamics. It states that at temperature of absolute zero, entropy remains zero. Absolute zero is the temperature at which the motion of an average atom or an average molecule is zero [2, 3]. Several examples of our daily activities can be described on the basis of these laws. These are [2–4]:  All types of vehicles that we used to see running on-roads every day, such as cars, motorbikes, trucks, or those that fly in air i.e., aeroplanes, or the ships that run on water; all work on the basis of the second law of thermodynamics.

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International Journal of Thermodynamics and Chemical Kinetics Vol. 2: Issue 2

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Chemical Composition in Atmosphere: An Introductory Approach for Students Amit Agnihotri Department of Chemical Engineering, ITM, Gwalior, India

Our atmosphere is divided into different strata above the earth’s surface. The region closest to earth’s surface is the troposphere that is extended upto 10–16 km above the surface. This layer or strata is followed by stratosphere which extends upto nearly 50 km.[1] Above it is the mesosphere region, which covers about 50–85 km from surface of the earth. Beyond the mesosphere lies the thermosphere which goes from 85–500 km away from the earth’s surface.[1]

Troposphere largely consists of gases viz., nitrogen and oxygen, carbon dioxide, and water vapor. Oxides of nitrogen and Sulphur, methane and some other trace gases are also found in this layer. The stratospheric region consists of less dense composition and is more exposed to radiation from the Sun. The molecules of this region therefore have more velocity and kinetic energy. The composition is rich in nitrogen and their oxides, oxygen, and ozone.[2,3]

The chemical composition in these layers varies considerably and so does the chemical reactions.

The third layer above the ground level is the mesosphere which consists of ions of molecules that were found in the layer beneath it i.e., stratosphere. This layer receives intense solar radiation and therefore the molecules here get ionized and exist as small ionized molecules, positive ions and electrons.

Fundamentally, atoms in the lithosphere undergo reduction reaction over time, while those in upper atmosphere are more prone to be oxidized. This is because atmospheric density decreases as we move up from ground level. Higher density at ground level means that there is more number of molecules available per unit volume of gas to interact with each other. Also, the temperature of gaseous substances transforms from room temperature to very cold and then to very hot and then very cold while moving from surface of the earth towards thermosphere. During this, the entire composition of gas change. The gaseous molecules experience change in their velocity and hence kinetic energy and undergo several collisions amongst each other.[2] This is why we find stable molecules at the surface and highly charged atoms or ions at the top (towards thermosphere).

The topmost layer, thermosphere, receives even more intense radiations of the Sun. The molecules exist as mixture of highly charged ions and atoms. Chemical reactions in the atmospheric layers can occur in any forms: gas phase collisions between the molecules, surfaces of particulate matter or in water droplets (aqueous phase).[1] As we move away from the earth’s surface, there is variation in the altitude, pressure and temperature. As we go up, temperature decreases till the end of troposphere, after which it begins to increase as the stratosphere arrives. With the further rise in altitude, temperature

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Office No-4, 1 Floor, CSC, Pocket-E, Mayur Vihar, Phase-2, New Delhi-110091, India E-mail: info@journalspub.com

20 mit icle b rt u S A Applied Mechanics r International Journal of Electro Mechanics and u Mechanical Behaviour International Journal of Machine Design and Yo Manufacturing

Mechanical Engineering

¬ International Journal of Thermal Energy and

¬ International Journal of Production Engineering ¬ International Journal of Industrial Engineering

« « «

Applications

International Journal of Mechanical Dynamics and Analysis International Journal of Fracture and damage Mechanics International Journal of Structural Mechanics and Finite Elements

and Design ¬ International Journal of Manufacturing and

Materials Processing ¬ International Journal of Mechanical Handling and

Automation 5 more...

Electronics and Telecommunication « International Journal of Radio Frequency Design « International Journal of VLSI Design and Technology « International Journal of Embedded Systems and Emerging

Technologies « International Journal of Digital Electronics « International Journal of Digital Communication and Analog

Chemical Engineering « International Journal of Renewable Energy and its

Commercialization « International Journal of Environmental Chemistry « International Journal of Agrochemistry « International Journal of Prevention and Control of Industrial

Pollution

5 more...

Signals

1 more...

Civil Engineering

Architecture « International Journal of Housing and Human Settlement

Planning « International Journal of Architecture and Infrastructure

Planning « International Journal of Rural and Regional Planning

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Development

« International Journal of Town Planning and Management

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Nursing « « « « «

Material Sciences and Engineering

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5 more...

Biotechnology « International Journal of Industrial Biotechnology and « « « «

IJTCK Jul–Dec 2016

Thermodynamics & Chemical Kinetics

2 more...

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International Journal of

Nanotechnology « International Journal of Applied Nanotechnology « International Journal of Nanomaterials and Nanostructures « International Journals of Nanobiotechnology

Chemistry

Physics « International Journal of Solid State Materials « International Journal of Optical Sciences