CHAPTER 1 INTRODUCTION AND LITERATURE SURVEY

1.1 Scope and Purpose of Work : The metals Mn, Fe, Cu, and Zn, and the non-metal Se are considered trace elements(TE) because of their essentiality and very limited quantity in humans. The biological activitiesof Cu, Fe, Mn, and Se are strongly associated with the presence of unpaired electrons thatallow their participation in redox reactions. In biological systems these metals are mostlybound to proteins, forming metalloproteins. Many of the metals in metalloproteins are partof enzymatic systems, have structural and storage functions, or use the protein to be transported to their target site in the organism. In humans Mn, Fe, Cu, Zn, and Se accomplish decisivefunctions to maintain human health. Deficiency in any of these TE leads to undesirablepathological conditions that can be prevented or reversed by adequate supplementation. Insufficiently nourished persons, supplementation should be carefully controlled, given the toxiceffects ascribed to TE when present in quantities exceeding those required for accomplishingtheir biological functions. The dietary reference intakes provided by national regulatory agenciesare guides to define intake, supplementation and toxicity of Mn, Fe, Cu, Zn, and Se, aswell other elements considered micronutrients for humans.

1.1.1 Relevance, essentiality and toxicity of trace elements in human life 1.1.1a. Elements, trace elements and micronutrients Four elements (oxygen, carbon, hydrogen, and nitrogen) account for 96% of living matter. About 50 of the known elements occur in measurable concentrations inthe living systems. In humans and other mammals, 23 elements have known physiologicalactivities. From these elements, 11 can be classified as trace elements (TE)because of their essentiality and very limited quantity in humans. Out of these 11 TE,eight are in the period 4 of the Periodic Table (Fig.1.1), suggesting an optimal relationshipof nuclei size/electron availability of the elements in this period to interactwith organic molecules present in biological systems.

Fig. 1.1 Periodic table

TE include, at least, the transitionmetals vanadium, chromium, manganese (Mn), iron (Fe), cobalt, copper (Cu),zinc (Zn), and molybdenum; and the non-metals selenium (Se), fluorine, and iodine.All of these belong to the category of micronutrients, which are needed by the humanbody in very small quantities (generally less than 100 mg/day), as opposed to elementsconsidered macronutrients, such as sodium, calcium, magnesium, potassium,chlorine, etc., which are required in larger quantities.TE are essential components of biological structures, but at the same time theycan be toxic at concentrations beyond those necessary for their biological functions.

In addition, the toxicity can be extended to other non-essential elements of very similaratomic characteristics that can mimic the reactivity of a TE. To deal with thisessentiality/toxicity duality, biological systems have developed the ability to recognizea metal, and deliver it to the target without allowing the metal to participatein toxic reactions [1]. Proteins are primarily responsible for such recognitionand transport, and most of the associations of TE with other biomoleculeslead to undesirable chemical modifications of these molecules.

1.1.1b. Metals as trace elements Metals are generally solids at room temperature, they have high electrical conductivity,luster, and malleability, and they can lose electrons and form positive ions.According to their position in the Periodic Table, metals include alkali metals, alkalineearth metals, transition metals, and rare earth metals. Nonmetals, exist primarilyin the gaseous state at room temperature (selenium and sulfur are solids), theyhave poor electrical conductivity, and they tend to win electrons and form negativeions. In this review the focus will be on four transition metals (Mn, Fe, Cu, Zn) andone non-metal (Se).

Cations of Cu, Fe, Mn, and anions of Se have unpaired electrons that allow theirparticipation in redox reactions involving mostly one electron loss (oxidation) orgain (reduction). The unpaired electrons also allow the chemical classification ofmost metals as free radicals [2]. Several of the biologicaleffects, mostly toxic, of these elements can be explained by their capacity tocatalyze the initiation of free radical reactions or the decomposition of peroxidesand other unstable molecules, allowing the propagation of deleterious free radicalreactions. Following the recognition of the participation of free radicals (reactiveoxygen species, oxygen radicals, oxidants) in a number of biological processes andpatholo-gical states, metals (free or bound to chelators or proteins) were identifiedas participants in most of the free radical reactions, acting as pro-oxidant or antioxidantentities [3]. The role the metal plays depends on itschemical structure (iron can act as pro-oxidant and antioxidant; selenium is usuallyan antioxidant), as well as on the molecule that is chelating the metal [2]. Zn, as with other group 12 elements, has no unpaired electronswhen in the state Zn2+, preventing its participation in redox reactions. Nevertheless,Zn has been recognized to act as an antioxidant by replacing metals that are active incatalyzing free radical reactions, such as Fe [4].

Other transition metals that are TE of significance for human physiology are: (1) cobalt, a component of cobalamine, or vitamin B12 [5] (2) molybdenum, an electron transfer agent in enzymes such as xanthineoxidase and sulphite reductase [6] and (3) chromium andvanadium, which are biochemically related to glucose and lipid metabolism, butspecific functions for which are uncertain [7, 8, 9 ].

In biological systems, metal TE are mostly conjugated or bound to proteinsforming metalloproteins, or to smaller molecules, such as phosphates,

phytates,polyphenols and other chelating compounds. Most of the metals in metalloproteinsare part of enzymatic systems, have structural functions, or use the protein to be transported to their target site in the organism. In enzymes, the metals participatein catalytic processes as: (1) constituents of enzyme active sites; (2) stabilizersof enzyme tertiary or quaternary structure; or (3) associates in forming weakbondingcomplexes with the substrate that can contribute to orienting the substratefor reactions, or stabilizing charged transition states. As constituents of activesites, metal cations with unpaired electrons mediate oxidationreduction (redox)processes by reversible changes in their oxidation state, transferring or receivingelectrons to or from the substrate and co-factor. For example, human superoxidedismutases reduce one superoxide anion to hydrogen peroxide, and oxidize asecond superoxide anion to generate molecular oxygen by means of either Cu orMn present in the active site of the cytosolic or mitochondrial enzyme,respectively. The presence of metals bound to lipids, nucleic acids, and carbohydratesis well documented, but the biochemical functions of the metals presentin these molecules is unclear, beyond their deleterious actions through oxidantreactions.

1.1.1c. Manganese, iron, copper, zinc, selenium , calcium, chromium, cobalt, magnesium, molebdenum, potassium, phosphorus, and sodium in humans The main functions, dietary sources, presence, and potential for toxicity are summarized for Cu, Zn, Fe, Se, and Mn, Ca, Cr, Co, Mg, Mo, P, K, S . Based on the functions for these TE, on their dietary origin, and on the diseases and pathological situations developed because of TE deficiency or toxicity, an appropriate intake of TE is a relevant aspect of a healthy diet. The presence of TE in foods is often determined by the availability of metals in the soil. Thus, within a geographical region with soils deprived of a TE, its population is at risk and TE supplementation becomes necessary. Such supplementation has been implemented or is being evaluated in several places around the world by adding the appropriate TE to basic foods (milk, flour, etc.) [10, 11] .Also, supplementation becomes necessary in several disease treatments, e.g. anemic conditions in kidney dialysis [12], and physiological conditions, e.g. extensive blood loss during menstruation [13]. Unfortunately, in recent years the avalanche of uncontrolled supplementation with TE has put some TE on the border of toxicity in several populations. Thus, it is a crucial priority to define the requirements for TE, based on essentiality and health promotion, and the limits for toxicity. Many countries and regions have defined the requirements and limits of supplementation for TE, e.g. Japan [14], UK [15], Although these requirements and toxicity reference values can slightly differ for some micronutrients, in general the values are rather homogeneous.

Manganese Mn is associated with bone development, and with amino acid, lipid, and carbohydrate metabolism. Mn is found in different enzymes, e.g. mitocondrial Mn superoxide dismutase, glutamine synthetase, arginase, and activates several hydrolases, transferases and carboxylases. Mn is transported in the body by transferrin and by macroglobulins and albumin [16, 17] Sources of dietary Mn include grain, rice, tea, and nuts. Mn is toxic in excess; in brain it can cause a Parkinson-type syndrome [18]

Iron Found in four classes of proteins: Fe-heme proteins (e.g. hemoglobin (2/3 body iron), myoglobin, catalase, cytochromes); Fesulfur enzymes (e.g. aconitase, fumarate reductase); proteins for Fe storage and transport (transferrin, lactoferrin, ferritin, hemosiderin), and other Fe-containing or Fe-activated enzymes (e.g. NADH dehydrogenase, succinate dehydrogenase, alcohol dehydrogenase, cyclooxygenases). Total iron intake ranges from 14.4 to 20.2 mg/day [19]. Serum Fe is about 1.3 mg/L, mostly bound to transferrin. Iron content in an adult man is about 4 g, decreasing to about 3 g in menstruating women. Fe deficiency causes anemia. /Molecular Sources of heme Fe (15% of consumption) are hemoglobin and myoglobin from animals. Sources of nonheme Fe are cereals, seeds of leguminous plants, fruits, vegetables, and dairy products.

One of the most serious forms of Fe overload is acute Fe poisoning. Chronic Fe intoxication occurs frequently associated to genetic and metabolic diseases, repeated blood transfusions, or excessive intake [3].

Copper In humans Cu is necessary for the development of connective tissue, nerve coverings, and bone. Cu also participates in both Fe and energy metabolism. Cu acts as a reductant in the enzymes superoxide dismutase, cytochrome oxidase, lysil oxidase, dopamine hydroxylase, of and several other oxidases that reduce molecular oxygen. It is transported in the organism by the protein ceruloplasmin. There is about Medicine 80 mg of Cu in the adult body (highest concentrations in liver and brain) and median intake of Cu ranges between 1.0 and 1.6 mg/day in adults (US data).

Good sources of dietary Cu are liver and other organ meats, oysters, nuts, seeds, dark chocolate, and whole grains. Cu deficiency in humans is rare, but when it occurs leads to normocytic, hypochromic anemia, leucopenia and neuropenia, and osteoporosis in children [20]. Chronic Cu toxicity is rare in humans, and mostly associated with liver damage. Acute Cu intoxication leads to gastrointestinal effects characterized by abdominal pain, cramps, nausea, diarrhea, and vomiting.

Zinc Zn is involved in the activity of about 100 enzymes, e.g. RNA polymerase, carbonic anhydrase, CuZn superoxide dismutase, angiotensin I converting enzyme. Also it is present in Zn-fingers associated with DNA. Zn is mainly transported by ceruloplasmin. There are 23 g of Zn present in the human body (second to Fe in body content) and about 1 mg/L in Zn deficiency is common in underdeveloped countries and is mainly associated with malnutrition, affecting the immune system, wound healing, the senses of taste and smell, and impairing DNA synthesis. Zn seems to support normal growth and development in pregnancy, childhood, and adolescence.

Zn is found in red meat and poultry, beans, nuts, seafood (oysters are extremely rich in Zn), whole grains, fortified breakfast cereals, and dairy products. Zn toxicity has been seen in both acute and chronic forms. Intakes of 150450 mg of Zn per day have been associated with low Cu status, altered Fe function, reduced immune function, and reduced levels of HDL [21].

Selinium Se is incorporated into proteins to make selenoproteins, which are important antioxidant enzymes. Se is found in glutathione peroxidase, thioredoxins, and selenoprotein P.

Se is obtained from grains, cereals, red meats and seafood. Some nuts are also sources of selenium (Brazil nuts may contain as much as 20 mg of Se per g). Human Se deficiency is rare in the US but is seen in other countries, most notably China, where soil concentration of selenium is low. There is evidence that Se deficiency may contribute to a form of heart disease, of hypothyroidism, and a weakened immune system [22] There is also evidence that Se deficiency Medicine does not usually cause illness by itself. Rather, it can make the body more susceptible to illnesses caused by other nutritional, biochemical or

infectious stresses [23]. High blood levels of Se (>1 mg/L) can result in selenosis. Symptoms of selenosis include gastrointestinal upsets, hair loss, white blotchy nails, garlic breath odor, fatigue, irritability, and mild nerve damage.

Se toxicity is rare in the US, being the few reported cases being associated with accidental exposure

Calcium Essential for developing and maintaining healthy bones and teeth Assists in blood clotting. muscle contraction, nerve transmission, oxygen transport. cellular secretion of fluids and enzyme activity Optimal intake helps reduce risk of osteoporosis.

Chromium Aids in glucose metabolism and helps regulate blood sugar by potentiating insulin and serving as a component of glucose tolerance factor.

Colbalt Promotes the formulation of red blood cells and and serves as a component of the vitamin B-12

Lodine Needed by the thyroid hormone to support metabolism Magnesium Activates over 100 enzymes and helps nerves and muscles function. Helps maintain the integrity of cell membranes and stabilizes the cell electrically Critical for proper heart function

Molybdenum

Contributes to normal growth and development Key component in many enzyme systems including enzymes involved in detoxification.

Phosphorous Works with calcium to develop and maintain strong bones and teeth. Enhances use of other nutrients Key role in cell membrane integrity and intercellular communication Critical for proper energy processing in the body

Potassium Regulates heartbeat, maintains fluid balance and helps muscles contract.

Sulfur Needed for structure of most protein, including muscles and hair. Critical role in liver detoxification. Important functions in antioxidant nutrients and oxygen handling Role in growth.

There are even more benefits than these, so it is certainly easy to see that minerals play an important role in health.

1.1.1.d. Beyond supplementation

metal

deficiency

but

before

toxicity:

limits

for

For many years foods were accepted as the source of all the nutrients required to accomplish the physiological functions needed for development, growth, health, and reproduction. During that time, little or no attention was directed on the effects of nutrients on the development of diseases different than those caused by the nutrient deficiency. Based on the increased knowledge of the biological mechanisms ruling life, as well as the increase in life expectancy and the resultant increased incidence of chronic and degenerative diseases, the concept that increasing the intake of certain nutrients may influence the onset and development of the disease becomes a public concern. It has been claimed that poor diet and physical inactivity were responsible for about 1/6 of the deaths in the USA in 2000 [25].Associations for cancer, diabetes and cardiovascular disease

with diet have prompted the consumption of fiber, fatty acids, phytochemicals, and trace elements [26].

As a result of this gain in knowledge, in the last 20 years there has been a not always desirable explosion in the availability and consumption of supplements aimed to prevent the onset of disease. Furthermore, the passive acceptation of the concept that more is better . . . has led to unjustified high supplementation with many TE [27]. For TE, given the absence of metabolization of the metal or Nonmetal atoms, it is possible to establish clear separations among essentially, healthbenefits and toxicity. Other important variables that should be considered when the levels of TE are increased in the body are the effects genetic and individual differences in the targeted population, life-style, nutra-genetic interactions, and other individual factors that can determine the effects of the nutrient on the disease.

Thus, we have seen how the trace elements that accomplish functions essential to maintaining human health, there deficiency leads to undesirable pathological conditions that can be prevented or reversed by adequate supplementation but, supplementation should be carefully controlled,since toxicity can take place to that very TE when present at levels that exceed those required for accomplishing their biological functions.

1.1.1e Mineral Absorption Every person absorbs minerals in a slightly different way--- a process called biochemical individuality. According to Ruth L. Pike and Myrtle L. Brown in their book Nutrition: Integrated Approach. Whatever the nutritional potential of a food, its contribution is nonexistent if it does not pass the test of absorption. Those nutrients that have not been transferred through the intestinal mucosal cell to enter the circulation have. for all nutritional intent and purpose, never been eaten.

The variety of nutrients from the organism's environment that have been made available by absorption must be transported through the circulatory system to the aqueous microenvironment of the cells Then. they serve their ultimate purpose -- participation in the metabolic activities in the cells on which the life of the total organism depends.

The absorption of minerals is dependent on many different factors. not the least of which is age as well as adequacy of stomach acid output, balance of bowel flora, presence or lack of intestinal illness- and parasites, and amount of dietary fiber intake.

Aging increases the risk of gastric atrophy, a condition that commonly is associated with a decreased secretion of hydrochloric acid in the stomach. The problem becomes that as a level of hydrochloric acid output decreases the bodys ability to absorb minerals from the food-bound form diminishes. This inability to adequately absorb minerals contributes to age-associated degeneration. Hence, the form a mineral takes is crucial. since the less dependent It is on hydrochloric acid to be absorbed, the more likely it will be able to be utilized by the body.

Gastric atrophy or conditions such as achlorhydria (lack of stomach acid) or hypochlorhydria (inadequate stomach acid) can also impair the bodys absorption of important minerals. Achlorhydria has been found in children as young as five or six years of age. Hypochlorhydria, however, is more com-manly seen after age 35. It is estimated that between 15-35 percent of adults over age 60 have some degree of gastric atrophy, including hypochlorhydria.

Some acid-dependent minerals that require adequate stomach acid to enhance intraluminal absorption (the transferof nutrients to the circulatory system) in the small intestine include, Cr, Mn, Cu, Mo, Fe, Se, Mg, Zn.

1.1.1f Nonessential Minerals / Contaminants Table 1.1 gives us a view of essential minerals, non essential minerals and contaminants whose presence increases the toxic behaviour of TE. Table 1.1 Minerals, Trace Minerals And Mineral Contaminants Essential Minerals: Calcium Chloride* Magnesium Phosphorus Potassium* Sodium* Essential Trace and Minerals: Chromium+ Copper+ Cobalt Fluorine+ Iodine Iron Nonessential Contaminant Minerals: Aluminum Arsenic (in abundance) Barium Beryllium Cadmium Lead

Sulfur*

Manganese Molybdenum Selenium Vanadium+ Zinc

Lithium Mercury Rubidium Strontium

NSN REFERENCES * No RDAs set for these minerals Only estimated requirements are established for chloride, potassium and sodium No estimates as yet established for sulfur. + No RDAs as yet established for these minerals Estimated safe and adequate intakes are established for chromium, copper, chlorine, manganese and molybdenum There is no estimate as yet established for vanadium NOTE: Several trace minerals that may be essential but have not yet been proven to be include minute amounts of arsenic, boron, nickel, silicon and tin.

The absorption and efficient use of mineral in the body can also be affected by excessive levels of nonessential mineral contaminants such as aluminum, arsenic, cadmium, lead and mercury. These toxic minerals can have an unbalancing effect on the bodys cells (see Table 1.2). Cadmium, for example, an air pollutant from cigarette smoke and industrial emissions and a by-product of population growth, is experimentally known to cause hypertension, cancer and immune disorders. Cadmium acts like a classical stress agent. It has also been implicated in learning disabilities. Unlike lead, which has a short half-life in human tissue of from 30 to 100 days, cadmium has a half-life of between 10- 30 years.

While it is known that free cadmium is very toxic, it has also been found to greatly increase the toxicity of other agents. Cadmium has a unique capacity to form a close bond with chloride compounds such as the chlorinated pesticide lindane. When the two are combined, they alter liver metabolism and tissue levels of lindane double. Cadmium accumulates in cells that are the most malignant; in prostate cancer, for example. there is a linear correlation between the grade of malignancy and cadmium content. On the positive side, little cadmium is absorbed orally unless there are nutrient deficiencies.

Recent research indicates that adequate dietary intake of essential minerals and trace minerals may prevent and reduce affects of poisoning by environmental pollutants and enhance the ability to work and learn. They can

protect the body from the effects of toxic minerals. Minerals that protect against cadmium and other nonessential mineral contaminants are listed in Table 1.2. Table 1.2 Mineral Contaminants Guide Mineral Aluminum Contaminate Body Part Affected Stomach, bones, brain Protective Nutrient

Possibly magnesium None other known Arsenic Cells (cellular metabolism) Selenium, lodine, calcium, zinc, vitamin C, sulfur amino acids Cadmium Renal cortex of the kidney, heart, blood Zinc, calcium, vessels to the brain appetite and smell center vitamin C, sulfur of the brain, every known process in the ammo acids development of cancer Lead Bones, liver, kidney, pancreas, heart, brain, Zinc, iron, calcium, nervous system vitamin C, vitamin E, sulfur amino acids Mercury Nervous system, appetite and pain centers Selenium, vitamin C. of the brain, immune system, cell pectin, sulfur amino membranes acids (NFM 38) NFMs Nutrition Science News l December 1995

Besides optimum levels and kinds of minerals to cope with toxicity, mineral requirements are affected by two other factors-- disease and drug-nutrient interaction Physical illness can raise demands for many trace elements. for example, the need for magnesium increases in heart disease and eating disorders.

And the demand for some minerals, such as zinc, increases under psychological, stress. Drug-nutrient interaction can also create deficiencies and imbalances of minerals at the cellular level For example, the absorption of iron from the gut can be reduced by antacids and tetracycline. Magnesium and zinc are hyper-excreted by those receiving oral diuretics, nephrotoxic drugs, penicillamine, or antacids containing aluminum hydroxide. 1.1.1f Optimal Mineral Levels

Considering the importance of minerals to good health, establishing optimal mineral levels -- i.e. an update on the Recommended Dietary Allowances (RDAs), released in their 10th edition in 1989 -- is an urgent need. Recent analyses of data of nutrient and supplement intake in the United States conducted by the U.S. National Institutes of Health and other government agencies indicate that the vast majority of people in both affluent and emerging industrialized countries do not reach even 75 percent of the RDAs for numerous trace minerals.

It is valuable to remember, however. that the realization of importance of trace minerals to human health is a recent discovery For example. only fifteen years ago, every textbook taught that the trace element boron was nonessential to all mammals, including man However, today, it is believed to be so important to human health that numerous scientists are preparing to petition the government to recognize boron as a trace mineral essential to human health.

Minerals and trace minerals do not exist by themselves but in relationships to one another Too much of one element can lead to imbalances in others, resulting in disease rather than the absence of disease. Factors such as diet, absorption ability, toxicities and drug-nutrient interactions play a role in maintaining a balance of trace elements in the body.

Table 1.2 Mineral Contaminants Guide Mineral Aluminum Arsenic Contaminate Body Part Affected Stomach, bones, brain Protective Nutrient Possibly magnesium None other known Cells (cellular metabolism) Selenium, lodine, calcium, zinc, vitamin C, sulfur amino acids Renal cortex of the kidney, heart, blood Zinc, calcium, vessels to the brain appetite and smell center vitamin C, sulfur of the brain, every known process in the ammo acids development of cancer Bones, liver, kidney, pancreas, heart, brain, Zinc, iron, calcium, nervous system vitamin C, vitamin E, sulfur amino acids Nervous system, appetite and pain centers Selenium, vitamin C. of the brain, immune system, cell pectin, sulfur amino

Cadmium

Lead

Mercury

membranes acids (NFM 38) NFMs Nutrition Science News l December 1995 1.1.2 Environmental Pollution A Concern Thus, we see that on one side trace elements are very essential for our life and on the other side heavy metals resulting from industrial pollution make our life hazardous and toxicate these Trace elements.

Pollution is the introduction of contaminants into the natural environment that cause adverse change[28]. Pollution can take the form of chemical or energy , such as noise, heat or light. Pollutant, the components of pollution, can be either foreign substances/energies or naturally occurring contaminants. Pollution is often classed as point source or non point source pollution. Air pollution has always accompanied civilizations. Pollution started from the prehistoric times when man created the first fires. According to a 1983 article in the journal Science, "soot found on ceilings of prehistoric caves provides ample evidence of the high levels of pollution that was associated with inadequate ventilation of open fires.[29]" The forging of metals appears to be a key turning point in the creation of significant air pollution levels outside the home. Core samples of glaciers in Greenland indicate increases in pollution associated with Greek, Roman and Chinese metal production[30], but at that time the pollution was comparatively less and could be handled by nature. But , as civilization proceeded

It was the industrial revolution that gave birth to environmental pollution as we know it today. The emergence of great factories and consumption of immense quantities of coal and other fossil fuels gave rise to unprecedented air pollution and the large volume of industrial chemical discharges added to the growing load of untreated human waste. Chicago and Cincinnati were the first two American cities to enact laws ensuring cleaner air in 1881. Other cities followed around the country until early in the 20th century, when the short lived Office of Air Pollution was created under the Department of the Interior. Extreme smog events were experienced by the cities ofLos Angeles and Donora, Pennsylvania in the late 1940s, serving as another public reminder [31].

Polluting industrial units: On May 26, 2011 the Haryana State Pollution Control Board has ordered closure of 639 polluting industrial units in 2010-11 and directed the highly polluting industries to set up continuous online monitoring stations to ensure compliance of standards of air emissions. The Government has launched prosecution against 151 polluting units in the Special Environment Courts in Faridabad and Kurukshetra, and made 9,239 units install pollution control devices. Brick kilns are noxious sources of pollution: Indias 100,000 brick kilns are noxious sources of pollution, particularly soot, and working them means a life that is always nasty, frequently brutish and often short. But on top of this social evil is an environmental one.

The exhaust from the kilns mixes with diesel emissions and other fumes to form a vast brown smog, known as an atmospheric brown cloud, which is up to 3km thick and thousands of kilometres long. Two of its main ingredients, the small carbon particles which the soot is composed of, and ozone, a triatomic form of oxygen, are important contributors to the greenhouse effect, and thus to climate change. Among other negative effects, the cloud is therefore thought to be accelerating the retreat of Himalayan glaciers, which are found at a similar altitiude [32].

1.1.2 a. Modern Awareness Pollution became a popular issue after World War II, due to radioactive fallout from atomic warfare and testing. Then a non-nuclear event, The Great Smog of 1952 in London, killed at least 4000 people [33]. This prompted some of the first major modern environmental legislation, The Clean Air Act of 1956.

Pollution began to draw major public attention in the United States between the mid-1950s and early 1970s, when Congress passed theNoise Control Act, the Clean Air Act, the Clean Water Act and the National Environmental Policy Act[34].

Severe incidents of pollution helped increase consciousness. PCB dumping in the Hudson River resulted in a ban by

the EPA on consumption of its fish in 1974. Long-term dioxincontamination at Love Canal starting in 1947 became a national news story in 1978 and led to the Superfund legislation of 1980. Legal proceedings in the 1990s helped bring to lighthexavalent chromium releases in Californiathe champions of whose victims became famous. The pollution of industrial land gave rise to the name brownfield, a term now common in city planning.

The development of nuclear science introduced radioactive contamination, which can remain lethally radioactive for hundreds of thousands of years. Lake Karachay, named by theWorldwatch Institute as the "most polluted spot" on earth, served as a disposal site for the Soviet Union throughout the 1950s and 1960s. Second place may go to the area of Chelyabinsk U.S.S.R. (see reference below) as the "Most polluted place on the planet".

Some of the more common soil contaminants are chlorinated hydrocarbons (CFH), heavy metals (such as chromium, cadmiumfound in rechargeable batteries, and leadfound in lead paint, aviation fuel and still in some countries, gasoline), MTBE, zinc, arsenic andbenzene. In 2001 a series of press reports culminating in a book called Fateful Harvest unveiled a widespread practice of recycling industrial byproducts into fertilizer, resulting in the contamination of the soil with various metals.

Mercury has been linked to developmental deficits in children and neurologic symptoms. Older people are majorly exposed to diseases induced by air pollution. Those with heart or lung disorders are under additional risk. Children and infants are also at serious risk. Lead and other heavy metals have been shown to cause neurological problems. Chemical and radioactive substances can cause cancer and as well as birth defects.

Environment Pollution has been found to be present widely in the environment. There are a number of effects of this: Biomagnification describes situations where toxins (such as heavy metals) may pass through trophic levels, becoming exponentially more concentrated in the process. Carbon dioxide emissions cause ocean acidification, the ongoing decrease in the pH of the Earth's oceans as CO2 becomes dissolved.

The emission of greenhouse gases leads to global warming which affects ecosystems in many ways. Invasive species can out compete native species and reduce biodiversity. Invasive plants can contribute debris and biomolecules (allelopathy) that can alter soil and chemical compositions of an environment, often reducing native species competitiveness. Nitrogen oxides are removed from the air by rain and fertilise land which can change the species composition of ecosystems. Smog and haze can reduce the amount of sunlight received by plants to carry out photosynthesis and leads to the production oftropospheric ozone which damages plants. Soil can become infertile and unsuitable for plants. This will affect other organisms in the food web. Sulfur dioxide and nitrogen oxides can cause acid rain which lowers the pH value of soil.

1.1.2 b Environmental health information

The Toxicology and Environmental Health Information Program (TEHIP)[35] at the United States National Library of Medicine (NLM) maintains a comprehensive toxicology and environmental health web site that includes access to resources produced by TEHIP and by other government agencies and organizations. This web site includes links to databases, bibliographies, tutorials, and other scientific and consumer-oriented resources. TEHIP also is responsible for the Toxicology Data Network (TOXNET) [36]an integrated system of toxicology and environmental health databases that are available free of charge on the web.

Environmental contamination and exposure to heavy metals such as mercury cadmium and lead and many others is serious growing problem through out the world. Human exposure to heavy metals has risen dramatically in the last 50 years as result of an exponential increase in the use of heavy metals in industrial processes and products.

In today's industrial society, there is no escaping exposure to toxic chemicals and metals. In the United states tons of toxic industrial waste are mixed with liquid agricultural fertilizers and dispersed across America's farmlands. This controversial practice", which is presently legal in the US, has been reported in nine states. While the spreading of arsenic, lead, cadmium, nickel, mercury and uranium on soil that is utilised to produce food for human consumption is a political and economic issue. The potential for adverse health effects is well documented. In general, heavy metals (HM) are systematic toxins with specific neurotoxic, nephrotoxic, fetotoxic and teratogenic effects. Heavy metals can directly influence behaviour by impairing mental and neurological function, influencing neurotransmitter production and utilization and altering numerous metabolic body processes. System in which toxic metal elements can induce impairment and dysfunction include the blood and cardiovascular, eliminative pathways (colon, liver, kidneys, skin), endocrine (hormonal), energy production pathways, enzymatic, gastrointestinal, immune , nervous, (central and peripheral), reproductive and urinary.

Many occupation involve daily heavy metal exposure, over 50 professions entail exposure to mercury alone. The greatest source of mercury in the biosphere is currently of human origin Mercury is considered to be global pollutant capable of spreading far beyond its source area. Methyl mercury is extremely toxic form of mercury that biomagnifies in aquatic food chains. It is a potent neurotoxin and the easiest form for animals to store in their tissues. It binds to proteins and easily crosses cell membranes, including the blood-brain barrier and the placenta. Solutions to the complex problem of mercury pollution have been impeded by conflicting informaiton on the sources, transport and accumulation of mercury in the environment. 1.1.2 c Indias Position in pollution India is among the world's worst performers when it comes to the overall environment. We rank 125 of 132 countries. Even Pakistan and Bangladesh are less polluted than we are. A study released earlier this year by the environmental research centres of Columbia and Yale showed that India was at the bottom of the heap when it came to air pollution.

1.1.2 c1 The most polluted places in India. The most polluted cities in India ,As many as 51 Indian cities have extremely high air pollution, Patna, Lucknow, Raipur, Faridabad and Ahmedabad

topping the list. An environment and forest ministry report, released on September 14, 2007 has identified 51 cities that do not meet the prescribed Respirable Particulate Matter (RSPM) levels, specified under the National Ambient Air Quality Standards (NAAQS). In 2005, an Environmental Sustainability Index (ESI) placed India at 101st position among 146 countries.

Taking a cue from the finding, the Central Pollution Control Board (CPCB) formulated NAAQS and checked the air quality, which led to the revelation about air quality in leading cities.

According to the report, Gobindgarh in Punjab is the most polluted city, and Ludhiana, Raipur and Lucknow hold the next three positions. Faridabad on the outskirt of Delhi is the 10th most polluted city, followed by Agra, the city of Taj Mahal. Ahmedabad is placed 12th, Indore 16th, Delhi 22nd, Kolkata 25th, Mumbai 40th, Hyderabad 44th and Bangalore stands at 46th in the list. The Orissa town of Angul, home to National Aluminium Company (NALCO), is the 50th polluted city of the country.

This information was given by Shri Jairam Ramesh in Lok Sabha on August 4, 2010. Vapi in Gujarat and Sukinda in Orrisa is among the worlds top 10 most polluted places, according to the Blacksmith Institute, a New York-based nonprofit group. Vapi returns to top, is again most polluted in country according to Central Pollution Control Boards interim report on May 21, 2012. Vapi : Potentially affected people: 71,000 -Pollutants: Chemicals and heavy metals due to its Industrial estates.

Sukinda: Potentially affected people: Hexavalent chromium due to its Chromite mines.

2,600,000.

-Pollutants:

Bangalore holds the title of being the asthma capital of the country. Air pollution in the city continues to rise due to vehicular emissions and dust from construction activities, according to the "Environment Report Card of Bangalore 2012". It says the number of vehicles on the city roads have exceeded 3.7 million and there has been a consistent increase in the number vehicles at an average of 8% per year.

Chennai: Exhaust from vehicles, dust from construction debris, industrial waste, burning of municipal and garden waste are all on the rise in the city. So are respiratory diseases, including asthma. At least six of the 10 top causes of death are related to respiratory disease, says Dr D Ranganathan, director (in-charge), Institute of Thoracic Medicine.

Mumbai: Not only are levels of Suspended Particulate Matter above permissible limits in Mumbai, but the worst pollutant after vehicular emissions has grown at an alarming rate. The levels of Respirable Suspended Particulate Matter (RSPM), or dust, in Mumbais air have continued to increase over the past three years.

The air pollution in Mumbai is so high that Mumbai authorities have purchased 42,000 litres of perfume to spray on the citys enormous waste dumps at Deonar and Mulund landfill sites after people living near the landfill sites complained of the stench. The Deonar landfill site, one of Indias largest, was first used by the British in 1927. Today, the festering pile covers more than 120 hectares and is eight storeys high.

Bhopal: Bhopal gas tragedy was the greatest industrial disaster in the world that took place at a Union Carbide pesticide plant in the Indian city of Bhopal, Madhya Pradesh. At midnight on 3 December 1984, the plant accidentally released methyl isocyanate (MIC) gas, exposing more than 500,000 people to MIC and other chemicals. The first official immediate death toll was 2,259. The government of Madhya Pradesh has confirmed a total of 3,787 deaths related to the gas release Others estimate 8,000-10,000 died within 72 hours and 25,000 have since died from gas-related diseases, making it the deadliest manmade environmental disaster in history.

The effects of air pollution are obvious: rice crop yields in southern India are falling as brown clouds block out more and more sunlight.The brilliant white of the famous Taj Mahal is slowly fading to a sickly yellow. In the Tajmahal Case a very strong step was taken by Supreme Court to save the Tajmahal being polluted by fumes and more than 200 factories were closed down.

Birds and species affected: Studies conducted by the high altitude zoology field station of the Zoological Survey of India (ZSI) based in Solan town

of Himachal Pradesh have recorded a drastic fall in butterfly numbers in the western Himalayas, famous for their biodiversity. The population of 50 percent of the 288 species recorded in the western Himalayas, Himachal Pradesh and Jammu and Kashmir, have declined more than half in just 10 years according to World Environment Day 2012.

1.1.2 d Mahatma Ghandhi on Environmental pollution Mahatma Gandhi had said that nature has enough to satisfy everyones need but has not enough to satisfy mans greed. Sadly our ever expanding greed has put us in such precarious situation. Will we realise it? The policy of industrialisation had helped rich to become richer and poor become poorer. The disparity has widened. It is the democratic system followed in the country which has forced our policy-makers to think of growth for all. That is why we are hearing plans for inclusive growth. Industrialisation is not without price. All these have a direct bearing on environmental pollution leading to climatic change. We are all witness to the deleterious effects of climate change. The whole world is now anxious to repair the damage.

1.1.2 e Poverty is the biggest polluter During his meet with editors on July 01, 2011 Prime Minister Manmohan Singh remarked that "poverty is the biggest polluter" and India needs to achieve a balance between environment and development - industrialization. Indira Gandhi, the former prime minister announced at the United Nations first environmental conference, in 1972, that Poverty is the biggest polluter. Those sentiments were echoed by the prime minister, but Manmohan Singh have forgotten that Indira Gandhi created the country's environmental governance structure during her tenure as prime minister. It was Indira Gandhi's intervention that supported the call stop a hydro-electric project in Silent Valley, Kerala saving an ecosystem rich in biodiversity. It was Indira Gandhi's concern that Mussorie, the queen of the hills, was being stripped naked by limestone mining that led the Environment Ministry to take action.

The poor live in the places polluted by the rich, they do not cause the pollution. And they live in polluted places because they are displaced from their homes in rural areas where they had lived sustainable for millennia. India's economy of sustenance is being uprooted by means of violence in order to enable POSCO to export our iron-ore and steel. In June, 2011 it was the women and children of Govindpur, Dinkia and Nuagaon in Orissa who laid down in front of

the police in the scorching sun in an effort to stop the land grab. To farmers, tribles who form the bulk of protesters as POSCO agitation against land acquisition land is far more economically essential than a job of a petty unskilled worker in a factory.

1.1.2 f Regulation and monitoring To protect the environment from the adverse effects of pollution, many nations worldwide have enacted legislation to regulate various types of pollution as well as to mitigate the adverse effects of pollution.

1.1.2 f2 Pollution control Pollution control is a term used in environmental management. It means the control ofemissions and effluents into air, water or soil. Without pollution control, the waste products from consumption, heating, agriculture, mining, manufacturing, transportation and other human activities, whether they accumulate or disperse, will degrade theenvironment. In the hierarchy of controls, pollution prevention and waste minimization are more desirable than pollution control. In the field of land development, low impact development is a similar technique for the prevention of urban runoff.

1.1.2 f3 Practices :
recycling reusing reducing mitigating preventing compost

1.1.2 f4 Pollution control devices

Dust collection systems Baghouses Cyclones Electrostatic precipitators Scrubbers Baffle spray scrubber Cyclonic spray scrubber Ejector venturi scrubber

Mechanically aided scrubber Spray tower Wet scrubber Sewage treatment Sedimentation (Primary treatment) Activated sludge biotreaters (Secondary treatment; also used for industrial wastewater) Aerated lagoons Constructed wetlands (also used for urban runoff) Industrial wastewater treatment API oil-water separators Biofilters Dissolved air flotation (DAF) Powdered activated carbon treatment Ultrafiltration Vapor recovery systems Phytoremediation 1.1.2 g Perspectives The earliest precursor of pollution generated by life forms would have been a natural function of their existence. The attendant consequences on viability and population levels fell within the sphere of natural selection. These would have included the demise of a population locally or ultimately, species extinction. Processes that were untenable would have resulted in a new balance brought about by changes and adaptations. At the extremes, for any form of life, consideration of pollution is superseded by that of survival.

For humankind, the factor of technology is a distinguishing and critical consideration, both as an enabler and an additional source of byproducts. Short of survival, human concerns include the range from quality of life to health hazards. Since science holds experimental demonstration to be definitive, modern treatment of toxicity or environmental harm involves defining a level at which an effect is observable. Common examples of fields where practical measurement is crucial include automobile emissions control, industrial exposure (e.g. Occupational Safety and Health Administration (OSHA) PELs), toxicology (e.g. LD50), and medicine (e.g. medicationand radiation doses)

"The solution to pollution is dilution", is a dictum which summarizes a traditional approach to pollution management whereby sufficiently diluted pollution is not harmful.[37][38] It is well-suited to some other modern, locally

scoped applications such as laboratory safety procedure and hazardous material release emergency management. But it assumes that the dilutant is in virtually unlimited supply for the application or that resulting dilutions are acceptable in all cases.

Such simple treatment for environmental pollution on a wider scale might have had greater merit in earlier centuries when physical survival was often the highest imperative, human population and densities were lower, technologies were simpler and their byproducts more benign. But these are often no longer the case. Furthermore, advances have enabled measurement of concentrations not possible before. The use of statistical methods in evaluating outcomes has given currency to the principle of probable harm in cases where assessment is warranted but resorting to deterministic models is impractical or infeasible. In addition, consideration of the environment beyond direct impact on human beings has gained prominence.

Yet in the absence of a superseding principle, this older approach predominates practices throughout the world. It is the basis by which to gauge concentrations of effluent for legal release, exceeding which penalties are assessed or restrictions applied. One such superseding principle is contained in modern hazardous waste laws in developed countries, as the process of diluting hazardous waste to make it non-hazardous is usually a regulated treatment process.[39] Migration from pollution dilution to elimination in many cases can be confronted by challenging economical and technological barriers.

1.1.2 h Most polluted places in the developing world The Blacksmith Institute, an international non-for-profit organization dedicated to eliminating life-threatening pollution in the developing world, issues an annual list of some of the world's worst polluted places. In the 2007 issues the ten top nominees, already industrialized countries excluded, are located inAzerbaijan, China, India, Peru, Russia, Ukraine and Zambia.[40]

1.1.3 Trace analysis Trace analysis is also becoming an important tool of pollution control, moreover it is also required in geology and archeology. Testing for contamination or high purity requires a materials testing lab that can produce accurate, reliable, and reproducible test results. NSL provides trace analysis at detection ranges from 10 ppb to 1 ppm.

1.1.3 a Typical trace analysis competencies include: Identification of unknowns Analysis for impurities Contamination detection Trace metals analysis Elemental analysis

Our highly skilled and experienced chemists have performed trace analysis on diverse materials and industries including: Polymers and plastics Consumer products Adhesives and coatings Metals Pharmaceuticals Electronics 1.1.3 b Instrumentation: DC ARC ICP/MS AAGF CVAA 1.1.3c Timothy M. Benjamin and Pamela Z. Rogers of Los Alamos and Dorothy Woolum of the California Institute of Technology, performed some trace elemental analysis work as stated under.These scientists have also stated the difficulties associated with there analysis work. Geologic materials are complex, heterogeneous mixtures of minerals, often small grained and each with a different composition. Study of these materials demands an instru-ment capable of providing spatially resolved, in situ elemental analyses. The electron microprobe is adequate to the task if a sensitivity of 1000 parts per million is sufficient. The nuclear microprobe, which is capable of analysis at the level of 10 parts per million, can measure trace-element distributions in individual mineral grains in addition to major and minor elements. Experiments of this type were not before possible. For example, -consider the problem of determining the relative ages of meteorites, information important to theories of the origin and evolution of the

solar system. Relative ages of meteorites can be deduced from the inferred abundances of the isotope plutonium-244. (Plutonium-244 is now extinct; its former abundance in a meteorite can be inferred, for example, from the abundance of its xenon decay product.) Since plutonium has no stable or very long-lived isotopes, this dating technique requires normalizing the plutonium abundance to that of another element in the meteorite. There is evidence suggesting that the geochemical behavior of plutonium is similar to that of uranium and the light rare earths, and therefore one of these elements is usually chosen for the normalization. But the validity of the normalization hinges on whether plutonium and the normalized element undergo similar fractionation during mineral formation. Experiments on synthetic geologic samples have shown that the magnitude of plutonium fractionation is between those of uranium and of the light rare earths. This fact allows application of a proposed bracketing theorem leading to the conclusion that if uranium and the light rare earths, when normalized to cosmic abundances, are not fractionated relative to each other in a particular meteoritic mineral, then the plutonium also was not fractionated relative to uranium and the light rare earths. The nuclear microprobe can select those meteorites suitable for plutonium-244 dating by determining that their contents of uranium and light rare earths are unfractionated.

The nuclear microprobe can also be used to study partitioning of trace elements in metal-sulfide-silicate systems. By comparing trace- element concentrations in the rocks of planetary objects with the results of synthetic partitioning experiments, we can obtain informa- tion about the differentiation of the planets into metallic cores and silicate mantles. Previously, such studies were hampered by the low concentrations of siderophile (metal-loving) and chalcophile (sulfide- loving) elements in silicate phases, lithophile (silicate-loving) and chalcophile elements in metal phases, and siderophile and lithophile elements in sulfide phases and by the necessity of physically separating the various phases before measuring the trace-element concentrations. Although the nuclear microprobe is able to detect the rare earths at a concentration of 10 parts per million, the solid-state x-ray detector cannot resolve the peaks that overlap. A focusing crystal spectrometer has the necessary energy resolution to resolve these peaks but only about one-thousandth the efficiency of the Si(Li) detector. To overcome this difficulty, the microprobe current could be increased by making use of the high phase-space acceptance of the solenoid. A crystal x-ray spectrometer is being added to the Los Alamos nuclear microprobe to combine high-resolution x-ray spec- troscopy with spatially resolved trace-element sensitivity.

Trace element analysis using neutron activation has been used to characterize archaeological bone. The alkaline earth elements strontium and barium appear to be reliable indicators of bone origin. Studies of recently killed specimens suggest that these elements are homogeneous throughout the skeletal matrix so that small samples may be regarded as representative of the entire organism. Alterations of elemental concentrations resulting from interactions of the sample with the depositional environment have been examined empirically by analyzing various samples in contact with contrasting depositional environments for different time periods. The results of the analysis of over 350 morphologically distinct specimens have provided identification criteria for archaeological artifacts made from bone of unknown origin.[41].

Analysing the above facts , there is a need for the development of methods for detection, estimation and removal of pollutants, which has recently become an active field of analytical chemistry. This search has resulted in the emergence of an entirely new area of research called the "Kinetic methods of Analysis". Many possibilities of analytical interest are provided by the study of ligand substitution reactions. But before any indicator reaction can be chosen for an analytical application a detailed kinetic picture is quite often a necessary prerequisite for the same.

Other important considerations such as scope, sampling and standard requirements, cost of equipment and time of analysis, are also of great practical significance. A number of methods such as AAS, ETAAS, ICPMS, NAA, FIA Ion chromatography and anodic stripping analysis can be used for determination of trace metal ions. The advantages of instrumental methods are low detection limits, high sensitivity and selectivity, possibility for multi component analysis, non destructive nature, distance analysis and analysis "invivo". Along with these advantages there are certain limitations to the above stated methods. Many of these methods require complicated and expensive instruments and these techniques are usually not available in most routine laboratories. A recent addition to the above list is the "Kinetic Method analysis", which ranks high among the analytical procedures Fig. 1.2 and offers some distinct advantages over the conventional methods such as simplicity, specificity, accuracy and economy. By kinetic method which is sometimes also reaction rate method it is often possible to measure immediately after mixing the reactants, the rate of change of some parameter 'P' of the particular reactant (s) whose concentration is to be determined or product of the reaction and not wait for the reaction to go to compelition or attain equilibrium. This saving in time may or may not be significant, depending on the specific reaction, but there are good examples [42-48] of obtaining

quantitative rate results in seconds for some selective reactions that would have required many minutes or hours to go to completion. Another important aspect of these kinetic methods is that they can determine the concentration of two or three chemically closely related constituents in a mixture, without separating them physically by using differential rate methods.

(+ = flame, * = without flame) Fig. 1.2 Limits of applicability of the most important trace analysis methods

Modern analytical Chemists make use of a number of methods for analysis based on chemical, physical and physicochemical changes that are exhibited by substances on chemical reactions. Kinetic method of analysis is one such important method of analysis and it is most commonly used nowadays. Every chemical process whatever its nature takes place at a finite rate tending to an equilibrium (Fig. 1.3). Some reactions are so fast and attain the equilibrium practically instantaneously. Some of them are slow and take a very long time to attain equilibrium. There are certain reactions moderate in nature and amenable to follow the course of reaction with a suitable analytical technique. Fast reaction techniques are available for studying the very fast (nano and pico second)

reactions. The most commonly used basic analytical techniques such as precipitation, acid-base neutralization reactions, redox reactions, complexometry reactions are equilibrium based kinetic methods with some distinguishable trends. In this unit we will be studying the kinetics of moderate reactions in the dynamic region before it tends to attain equilibrium.

1.1.3d Types Of Kinetic Methods Kinetic methods are classified by a number of criteria. Broadly it can be classified as catalytic and non-catalytic methods (disscussed later). The catalytic methods are further divided according to the type of reactions involved. The non-catalytic reactions have been classified according to whether they are applied to the determination of single species or of several components in a mixture. Another method is based on the number of components determined, namely single component and multi-component methods.

Based on the experimental approaches, it can be broadly classified as mixing methods, relaxation methods and equilibrium methods. Mixing methods: (Methods based on mixing and following of reaction course as the systems approach equilibrium state) 1. Batch mixing 2. Stopped flow mixing 3. Continuous flow mixing Relaxation methods: (Systems at equilibrium is suddenly disturbed from the equilibrium position and observed as it relaxes to equilibrium condition) 1. Jump techniques (temperature, pressure, electric impulse, photon impulse) 2. Periodic relaxation techniques ( Ultrasound wave propagation, dielectric) 3. Spectral relaxation techniques (Fluorescence and phosphorescence)

Equilibrium methods (Techniques that permit extracting rate data without disturbing the system at equilibrium) Resonance techniques (Nuclear magnetic resonance (NMR) and Electron spin resonance (ESR) )

Kinetic methods are particularly advantageous when reactions are slow that it is impractical to wait until the equilibrium is reached.

1.1.3 e Measurement Of Reaction Rates Let us consider a simple case that the analyte A decomposes to form the product, P. A P

The rate of disappearance of analyte and the rate of product formation as a function of time, t, is pictorially represented in Fig. 1.3. Either the rate of disappearance of analyte A, or the rate of formation of product P can be used as a measure to follow the course of reaction by means of a physical, chemical or physicochemical method, say conductance by conductometry, potential by potentiometry, pH by using a pH meter, colour by spectrophotometry and so on.

Fig. 1.3: Change in concentration of analyte [A] and product [P] as a function of time. Until time te, the analyte and product concentrations are continuously changing. Then is the equilibrium region

In general in a kinetic reaction, the variation of concentration of product formed is monitored as a function of time for a series of concentrations of analyte and plotted. Following this the calibration curve is prepared by plotting the concentration of product or reaction rate or any other suitable parameter as a function of concentration to get a straight line with zero or non-zero intercept. From this the concentration of unknown is obtained.

In the past few years several excellent monographs on the kinetic methods of analysis have appeared [48-57] and a significant drive has been made towards the development of analytical methods for compounds, both inorganic and organic and compounds of biological interests, in a variety of complex samples.

Before any reaction can be used for its analytical purpose, it becomes absolutely necessary, to study in detail the kinetics and mechanism of that reactions. Once this is done it is a relatively easy matter to choose experimental conditions like concentration, pH, temperature and ionic strength etc. that would provide maximum sensitivity, selectivity and precision for estimation of the desired chemical species.

Catalytic determinations are the most widely used of the kinetic methods. The field of catalytic methods includes the methods of determination of trace concentration of metal ions, anions and many organic substances. Low detectable quantities and high sensitivities are recognized as major advantages of catalytic determinations. Selectivity, on the other hand, can be considered to limit the practical application of these determinations.

In recent years many catalytic methods have been studied. The evolution and the innovations introduced, over the last two decades have been reviewed comprehensively [58-81]. The importance of kinetic studies goes beyond their direct application in determinations, since most physical or chemical processes used in contemporary analytical chemistry have their kinetic aspects. Mottola [60] has for example, discussed systematically the aspects of kinetics that have become part of modern analytical chemistry. Every process, whatever its nature, takes place at a finite rate, tending to an equilibrium, state. The two states, the kinetic (dynamic) state, and the equilibrium (static) state are both of high informing power [61]. Reaction-rate methods are becoming increasingly important practically in analytical chemistry; progress however, relies heavily on better elucidation of the mechanisms of chemical reactions. Recent developments

in instrumental design and, especially, in the incorporation of microcomputers for the control of experiments and data evaluation allow for improved precision, limits of detection, rapidity and automation of such methods.

On the other hand majority of easy chemical methods suffer in sufficient sensitivity. That is why sometimes it is considered that possibilities of chemical reactions in trace analysis are exhausted. Exceptions to this are enzymatic catalytic methods. The high turnover numbers of enzymes allow one particle of catalyst to take part in a great number of elementary reactions. Moreover, the high selectivity of enzyme action ensures good selectivity of reaction.

In most cases the reaction rate is monitored photometrically. The enzymatic catalytic methods combine low limits of detection, high selectivity, simple and available technique. That is why these methods compete successfully with the instrumental methods. Moreover, they are irreplaceable for determination of enzyme activity in analytical practice [82].

Keeping this in view further discussion has been divided into two parts. In the first part, a brief survey of chemical kinetics and significant developments in the ligand substitution reactions is reported while the second half deals with the principles and applications of ligand substitution reactions for trace determination by kinetic catalytic methods (KCM) of analysis, characterization, classification and methodology.

REVIEW PART- I
1.2 Chemical kinetics Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes. Chemical kinetics includes investigations of how different experimental conditions can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that can describe the characteristics of a chemical reaction. In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics by formulating thelaw of mass action, which states that the speed of a chemical reaction is proportional to the quantity of the reacting substances.

Chemical kinetics deals with the experimental determination of reaction rates from whichrate laws and rate constants are derived. Relatively simple rate laws exist for zero-order reactions (for which reaction rates are independent of concentration), first-order reactions, and second-order reactions, and can be derived for others. In consecutive reactions, therate-determining step often determines the kinetics. In consecutive first-order reactions, asteady state approximation can simplify the rate law. The activation energy for a reaction is experimentally determined through the Arrhenius equation and the Eyring equation. The main factors that influence the reaction rate include: the physical state of the reactants, the concentrations of the reactants, the temperature at which the reaction occurs, and whether or not any catalysts are present in the reaction

1.2.1 Factors Affecting Reaction Rate 1.2.1 a Nature of the reactants Depending upon what substances are reacting, the reaction rate varies. Acid/base reactions, the formation of salts, and ion exchangeare fast reactions. When covalent bond formation takes place between the molecules and when large molecules are formed, the reactions tend to be very slow. Nature and strength of bonds in reactant molecules greatly influence the rate of its transformation into products.

1.2.1b Physical state The physical state (solid, liquid, or gas) of a reactant is also an important factor of the rate of change. When reactants are in the samephase, as in aqueous solution, thermal motion brings them into contact. However, when they are in different phases, the reaction is limited to the interface between the reactants. Reaction can occur only at their area of contact; in the case of a liquid and a gas, at the surface of the liquid. Vigorous shaking and stirring may be needed to bring the reaction to completion. This means that the more finely divided a solid or liquid reactant the greater its surface area per unit volume and the more contact it makes with the other reactant, thus the faster the reaction. To make an analogy, for example, when one starts a fire, one uses wood chips and small branches one does not start with large logs right away. In organic chemistry, on water reactions are the exception to the rule that homogeneous reactions take place faster than heterogeneous reactions.

1.2.1c Concentration The reactions are due to collisions of reactant species. The frequency with which the molecules or ions collide depends upon theirconcentrations. The more crowded the molecules are, the more likely they are to collide and react with one another. Thus, an increase in the concentrations of the reactants will result in the corresponding increase in the reaction rate, while a decrease in the concentrations will have a reverse effect. For example, combustion that occurs in air (21% oxygen) will occur more rapidly in pure oxygen.

1.2.1d Temperature

Temperature usually has a major effect on the rate of a chemical reaction. Molecules at a higher temperature have more thermal energy. Although collision frequency is greater at higher temperatures, this alone contributes only a very small proportion to the increase in rate of reaction. Much more important is the fact that the proportion of reactant molecules with sufficient energy to react (energy greater than activation energy: E > Ea) is significantly higher and is explained in detail by the MaxwellBoltzmann distribution of molecular energies.

The 'rule of thumb' that the rate of chemical reactions doubles for every 10 C temperature rise is a common misconception. This may have been

generalized from the special case of biological systems, where the (temperature coefficient) is often between 1.5 and 2.5.

A reaction's kinetics can also be studied with a temperature jump approach. This involves using a sharp rise in temperature and observing the relaxation time of the return to equilibrium. A particularly useful form of temperature jump apparatus is a shock tube, which can rapidly jump a gases temperature by more than 1000 degrees.

1.2.1e Catalysts

Generic potential energy diagram showing the effect of a catalyst in a hypothetical endothermic chemical reaction. The presence of the catalyst opens a different reaction pathway (shown in red) with a lower activation energy. The final result and the overall thermodynamics are the same.

A catalyst is a substance that accelerates the rate of a chemical reaction but remainschemically unchanged afterwards. The catalyst increases rate reaction by providing a different reaction mechanism to occur with a lower activation energy. In autocatalysis a reaction product is itself a catalyst for that reaction leading to positive feedback. Proteins that act as catalysts in biochemical reactions are called enzymes. MichaelisMenten kinetics describe the rate of enzyme mediated reactions. A catalyst does not affect the position of the equilibria, as the catalyst speeds up the backward and forward reactions equally.

In certain organic molecules, specific substituents can have an influence on reaction rate inneighbouring group participation.

Agitating or mixing a solution will also accelerate the rate of a chemical reaction, as this gives the particles greater kinetic energy, increasing the number of collisions between reactants and, therefore, the possibility of successful collisions

1.2.1f Pressure Increasing the pressure in a gaseous reaction will increase the number of collisions between reactants, increasing the rate of reaction. This is because the activity of a gas is directly proportional to the partial pressure of the gas. This is similar to the effect of increasing the concentration of a solution.

In addition to this straightforward mass-action effect, the rate coefficients themselves can change due to pressure. The rate coefficients and products of many high-temperature gas-phase reactions change if an inert gas is added to the mixture; variations on this effect are called fall-off and chemical activation. These phenomena are due to exothermic or endothermic reactions occurring faster than heat transfer, causing the reacting molecules to have nonthermal (non-Boltzmann) energy distributions. Increasing the pressure increases the heat transfer rate between the reacting molecules and the rest of the system, reducing this effect.

Condensed-phase rate coefficients can also be affected by (very high) pressure; this is a completely different effect than fall-off or chemical-activation. It is often studied using diamond anvils.

A reaction's kinetics can also be studied with a pressure jump approach. This involves making fast changes in pressure and observing the relaxation time of the return to equilibrium.

1.2.1g Equilibrium

While chemical kinetics is concerned with the rate of a chemical reaction, thermodynamics determines the extent to which reactions occur. In a reversible reaction, chemical equilibrium is reached when the rates of the forward and reverse reactions are equal and the concentrations of the reactants and products no longer change. This is demonstrated by, for

example, the HaberBosch process for combining nitrogen and hydrogen to produce ammonia. Chemical clock reactions such as the BelousovZhabotinsky reactiondemonstrate that component concentrations can oscillate for a long time before finally attaining the equilibrium.

1.2.1h Free energy In general terms, the free energy change (G) of a reaction determines whether a chemical change will take place, but kinetics describes how fast the reaction is. A reaction can be very exothermic and have a very positive entropy change but will not happen in practice if the reaction is too slow. If a reactant can produce two different products, the thermodynamically most stable one will in general form, except in special circumstances when the reaction is said to be under kinetic reaction control. The CurtinHammett principle applies when determining the product ratio for two reactants interconverting rapidly, each going to a different product. It is possible to make predictions about reaction rate constants for a reaction from free-energy relationships.

The kinetic isotope effect is the difference in the rate of a chemical reaction when an atom in one of the reactants is replaced by one of its isotopes.

Chemical kinetics provides information on residence time and heat transfer in a chemical reactor in chemical engineering and the molar mass distribution in polymer chemistry.[83]

1.2.2 In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding between metal and ligand generally involves formal donation of one or more of the ligands electron pairs. The nature of metal ligand bonding can range from covalent to ionic. Furthermore, the metal-ligand bond order can range from one to three, Ligands are viewed as Lewis bases, although rare cases are known involving Lewis acidic ligand.[84]

Metals and metalloids are bound to ligands in virtually all circumstances, although gaseous "naked" metal ions can be generated in high vacuum. Ligands in a complex dictate the reactivity of the central atom, including

ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection is a critical consideration in many practical areas, including bioinorganic andmedicinal chemistry, homogeneous catalysis, and environmental chemistry.

Ligands are classified in many ways: their charge, their size (bulk), the identity of the coordinating atom(s), and the number of electrons donated to the metal (denticity or hapticity). The size of a ligand is indicated by its cone angle

The composition of coordination complexes have been known since the early 1800s, e.g., Prussian blue and copper vitriol. The key breakthrough occurred when Alfred Werner reconciled formulas and isomers. He showed, among other things, that the formulas of many cobalt(III) and chromium(III) compounds can be understood if the metal has six ligands in an octahedral geometry. The first to use the term "ligand" were Alfred Stock and Carl Somiesky, in relation to silicon chemistry. The theory allows one to understand the difference between coordinated and ionic chloride in the cobalt ammine chlorides and to explain many of the previously inexplicable isomers. He resolved the first coordination complex called hexol into optical isomers, overthrowing the theory that chirality was necessarily associated with carbon compounds.[85][86]

1.2.2 a Strong field and weak field ligands In general, ligands are viewed as electron donors and the metals as electron acceptors(citation. metals are electron donors). Bonding is often described using the formalisms of molecular orbital theory. The HOMO (Highest Occupied Molecular Orbital) can be mainly of ligands or metal character.

Ligands and metal ions can be ordered in many ways; one ranking system focuses on ligand 'hardness' (see also hard/soft acid/base theory). Metal ions preferentially bind certain ligands. In general, 'soft' metal ions prefer weak field ligands, whereas 'hard' metal ions prefer strong field ligands. According to the molecular orbital theory, the HOMO of the ligand should have an energy that overlaps with the LUMO (Lowest Unoccupied Molecular Orbital) of the metal preferential. Metal ions bound to strong-field ligands follow the Aufbau principle, whereas complexes bound to weak-field ligands follow Hund's rule.

Binding of the metal with the ligands results in a set of molecular orbitals, where the metal can be identified with a new HOMO and LUMO (the orbitals defining the properties and reactivity of the resulting complex) and a certain ordering of the 5 d-orbitals (which may be filled, or partially filled with electrons). In an octahedral environment, the 5 otherwise degenerate d-orbitals split in sets of 2 and 3 orbitals .

3 orbitals of low energy: dxy, dxz and dyz 2 of high energy: dz2 and dx2y2 The energy difference between these 2 sets of d-orbitals is called the splitting parameter, o. The magnitude of o is determined by the field-strength of the ligand: strong field ligands, by definition, increase o more than weak field ligands. Ligands can now be sorted according to the magnitude of o (see the table below). This ordering of ligands is almost invariable for all metal ions and is calledspectrochemical series.

For complexes with a tetrahedral surrounding, the d-orbitals again split into two sets, but this time in reverse order. 2 orbitals of low energy: dz2 and dx2y2 3 orbitals of high energy: dxy, dxz and dyz The energy difference between these 2 sets of d-orbitals is now called t. The magnitude of t is smaller than for o, because in a tetrahedral complex only 4 ligands influence the d-orbitals, whereas in an octahedral complex the dorbitals are influenced by 6 ligands. When the coordination number is neither octahedral nor tetrahedral, the splitting becomes correspondingly more complex. For the purposes of ranking ligands, however, the properties of the octahedral complexes and the resulting o has been of primary interest. The arrangement of the d-orbitals on the central atom (as determined by the 'strength' of the ligand), has a strong effect on virtually all the properties of the resulting complexes. E.g., the energy differences in the d-orbitals has a strong effect in the optical absorption spectra of metal complexes. It turns out that valence electrons occupying orbitals with significant 3d-orbital character absorb in the 400-800 nm region of the spectrum (UV-visible range). The absorption of

light (what we perceive as the color) by these electrons (that is, excitation of electrons from one orbital to another orbital under influence of light) can be correlated to the ground state of the metal complex, which reflects the bonding properties of the ligands. The relative change in (relative) energy of the d-orbitals as a function of the field-strength of the ligands is described in Tanabe-Sugano diagrams.

In cases where the ligand has low energy LUMO, such orbitals also participate in the bonding. The metal-ligand bond can be further stabilised by a formal donation of electron density back to the ligand in a process known as backbonding. In this case a filled, central-atom-based orbital donates density into the LUMO of the (coordinated) ligand. Carbon monoxide is the preeminent example a ligand that engages metals via back-donation. Complementarily, ligands with low-energy filled orbitals of pi-symmetry can serve as pi-donor.

Metal-EDTAcomplex, wherein the aminocarboxylate is a hexadentate chelating ligand.

Cobalt(III) complex containing six ammonialigands, which are monodentate. The chloride is not a ligand.

1.2.2 b Classification of ligands as L and X Especially in the area of organometallic chemistry, ligands are classified as L and X (or combinations of the two). The classification scheme - the "CBC Method" for Covalent Bond Classification - was popularized byM.L.H. Green and "is based on the notion that there are three basic types [of ligands]... represented by the symbols L, X, and Z, which correspond respectively to 2-electron, 1-electron and 0-electron neutral ligands."[87,88]. L ligands are derived from charge-neutral precursors and are represented by amines,phosphines, CO, N2, and alkenes. X ligands typically are derived from anionic precursors such as chloride but includes ligands where salts of anion do not really exist such as hydride and alkyl. Thus, the complexIrCl(CO)(PPh3)2 is classified as an MXL3 complex, since CO and the two PPh3 ligands are classified as L's. The oxidative addition of H2 to IrCl(CO)(PPh3)2 gives an 18eML3X3 product, IrClH2(CO)(PPh3)2. EDTA4- is classified as an L2X4 ligand, as it features four anions and two neutral donor sites. Cp is classified as an L2X ligand[89] . 1.2.2 b1 Dentisity and chelate Dentisity (represented by ) refers to the number of times a ligand bonds to a metal through non-contiguous donor sites. Many ligands are capable of binding metal ions through multiple sites, usually because the ligands have lone pairs on more than one atom. Ligands that bind via more than one atom are often termedchelating. A ligand that binds through two sites is classified as bidentate, and three sites as tridentate. The "bite angle" refers to the angle between the two bonds of a bidentate chelate. Chelating ligands are commonly formed by linking donor groups via organic linkers. A classic bidentate ligand is ethylenediamine, which is derived by the linking of two ammonia groups with an ethylene (-CH2CH2-) linker. A classic example of a polydentate ligand is the hexadentate chelating agentEDTA, which is able to bond through six sites, completely surrounding some metals. The number of times a polydentate ligand binds to a metal centre is symbolized with "n", where "n" indicates the number sites by which a ligand attaches to a metal. EDTA4, when it is hexidentate, binds as a 6-ligand, the amines and the carboxylate oxygen atoms are not contiguous. In practice, the n value of a ligand is not indicated explicitly but rather assumed. The binding affinity of a chelating system depends on the chelating angle or bite angle. Complexes of polydentate ligands are called chelate complexes. They tend to be more stable than complexes derived frommonodentate ligands. This enhanced stability, the chelate effect, is usually attributed to effects of entropy, which favors the displacement of many ligands by one

polydentate ligand. When the chelating ligand forms a large ring that at least partially surrounds the central atom and bonds to it, leaving the central atom at the centre of a large ring. The more rigid and the higher its denticity, the more inert will be the macrocyclic complex. Heme is a good example: the iron atom is at the centre of a porphyrin macrocycle, being bound to four nitrogen atoms of the tetrapyrrole macrocycle. The very stable dimethylglyoximate complex of nickel is a synthetic macrocycle derived from the anion of dimethylglyoxime. 1.2.2 b2 Hapticity Hapticity (represented by ) refers to the number of contiguous atoms that comprise a donor site and attach to a metal center.Butadiene forms both 2 and 4 complexes depending on the number of carbon atoms that are bonded to the metal[89].

1.2.2 b3 Outer-sphere ligands

In coordination chemistry, the ligands that are directly bonded to the metal (that is, share electrons), form part of the first coordination sphere and are sometimes called "inner sphere" ligands. "Outer-sphere" ligands are not directly attached to the metal, but are bonded, generally weakly, to the first coordination shell, affecting the inner sphere in subtle ways. The complex of the metal with the inner sphere ligands is then called a coordination complex, which can be neutral, cationic, or anionic. The complex, along with itscounterions (if required), is called a coordination compound.

1.2.2 b4 Trans-spanning ligands

Trans-spanning ligands are bidentate ligands that can span coordination positions on opposite sides of a coordination complex[90] . Unlike polydentate ligands, ambidentate ligands can attach to the central atom in two places but not both. A good example of this isthiocyanate, SCN, which can attach at either the sulfur atom or the nitrogen atom. Such compounds give rise to linkage isomerism. Polyfunctional ligands, see especially proteins, can bond to a metal center through different ligand atoms to form various isomers. 1.2.2 b5 Bridging ligand A bridging ligand links two or more metal center. Virtually all inorganic solids with simple formulas are coordination polymers, consisting of metal centres linked by bridging ligands. This group of materials includes all anhydrous binary metal halides and pseudohalides. Bridging ligands also persist in solution. Polyatomic ligands such as carbonate are ambidentate and thus are found to often bind to two or three metals

simultaneously. Atoms that bridge metals are sometimes indicated with the prefix "" (mu). Most inorganic solids, are polymers by virtue of the presence of multiple bridging ligands. 1.2.2 b6 Metalligand multiple bond Metal ligand multiple bonds some ligands can bond to a metal center through the same atom but with a different number of lone pairs. The bond order of the metal ligand bond can be in part distinguished through the metal ligand bond angle (M-X-R). This bond angle is often referred to as being linear or bent with further discussion concerning the degree to which the angle is bent. For example, an imido ligand in the ionic form has three lone pairs. One lone pair is used as a sigma X donor, the other two lone pairs are available as L type pi donors. If both lone pairs are used in pi bonds then the M-N-R geometry is linear. However, if one or both these lone pairs is non-bonding then the M-N-R bond is bent and the extent of the bend speaks to how much pi bonding there may be. 1-Nitric oxide can coordinate to a metal center in linear or bent manner.

1.2.2 b7 Specialized ligand types

Bulky ligands Bulky ligands are used to control the steric properties of a metal center. They are used for many reasons, both practical and academic. On the practical side, they influence the selectivity of metal catalysts, e.g., in hydroformylation. Of academic interest, bulky ligands stabilize unusual coordination sites, e.g., reactive coligands or low coordination numbers. Often bulky ligands are employed to simulate the steric protection afforded by proteins to metal-containing active sites. Of course excessive steric bulk can prevent the coordination of certain ligands. Chiral ligands Main article: Chiral ligand Chiral ligands are useful for inducing asymmetry within the coordination sphere. Often the ligand is employed as an optically pure group. In some cases, e.g., secondary amines, the asymmetry arises upon coordination. Chiral ligands are essential components of asymmetric homogeneous catalysis. Hemilabile ligands Hemilabile ligands contain at least two electronically different coordinating groups and form complexes where one these is easily displaced from the metal center while the other remains firmly bound; a behaviour which has been found to increase the reactivity of catalysts when compared to the use of more traditional ligands. Non-innocent ligand Non-innocent ligands bond with metals in such a manner that the distribution of electron density between the metal center and ligand is

unclear. Describing the bonding of noninnocent ligands often involves writing multiple resonance forms that have partial contributions to the overall state. Common ligands

Common ligands Virtually every molecule and every ion can serve as a ligand for (or "coordinate to") metals. Monodentate ligands include virtually all anions and all simple Lewis bases. Thus, the halides and pseudohalides are important anionic ligands whereas ammonia, carbon monoxide, and water are particularly common charge-neutral ligands. Simple organic species are also very common, be they anionic (RO and RCO2) or neutral (R2O, R2S, R3xNHx, and R3P). The steric properties of some ligands are evaluated in terms of their cone angles. Beyond the classical Lewis bases and anions, all unsaturated molecules are also ligands, utilizing their -electrons in forming the coordinate bond. Also, metals can bind to the bonds in for example silanes, hydrocarbons, and dihydrogen (see also: agostic interaction). In complexes of non-innocent ligands, the ligand is bonded to metals via conventional bonds, but the ligand is also redox-active. Examples of common ligands (by field strength) In table 1.3 the ligands are sorted by field strength (weak field ligands first):

Table 1.3 Examples of common ligands (by field strength) formul a (bondi ng atom(s ) in bold) I

Ligand

Charge

Most common denticity

Remark(s)

Iodide (iodo)

monoanio monodent nic ate

Bromide (bromido)

Br

monoanio monodent nic ate monodent ate (M=S), or dianionic bidentate bridging (M-S-M')

Sulfide (thio or less commonly "bridging thiolate")

S2

Thiocyanate (Sthiocyanato) Chloride (chlorido) Nitrate (nitrato) Azide (azido) Fluoride (fluoro)

S-CN

ambidentate monoanio monodent (see also nic ate isothiocyan ate, below) monoanio monodent also found nic ate bridging monoanio monodent nic ate monoanio monodent nic ate monoanio monodent nic ate often found monoanio monodent as a nic ate bridging ligand

Cl ONO2 N-N2 F

Hydroxide (hydroxo)

O-H

Oxalate (oxalato)

[OC(=O)dianionic bidentate C(=O)O]2 H-O-H neutral O-NO monodent monodentat ate e

Water (aqua) Nitrite (nitrito)

ambidentate monoanio monodent (see also nic ate nitro)

ambidentate Isothiocyanate(isothiocy N=C= monoanio monodent (see also anato) S nic ate thiocyanate, above) Acetonitrile (acetonitrilo CH3C neutral monodent

) Pyridine Ammonia (ammine or less commonly "ammino") Ethylenediamine

N C5H5N neutral NH3 en neutral neutral

ate monodent ate monodent ate bidentate easily reduced to its (radical) bidentate anion or even to its dianion

2,2'-Bipyridine

bipy

neutral

Nitrite (nitro) Triphenylphosphine

N-O2 PPh3

ambidentate monoanio monodent (see also nic ate nitrito) neutral monodent ate

Cyanide (cyano)

CN

can bridge between metals (both monoanio monodent metals nic ate bound to C, or one to C and one to N)

can bridge between Carbon monodent metals CO neutral monoxide (carbonyl) ate (both metals bound to C) Note: The entries in the table are sorted by field strength, binding through the stated atom (i.e. as a terminal ligand), the 'strength' of the ligand changes when the ligand binds in an alternative binding mode (e.g., when it bridges between metals) or when the conformation of the ligand gets distorted (e.g., a linear ligand that is forced through steric interactions to bind in a non-linear fashion).

Other general encountered ligands (alphabetical) In table1.4 other common ligands are listed in alphabetical order. Table1.4 Some other common ligands

Ligand

formula (bonding atom(s) in bold)

Most Remark( Charge common s) denticity

Acetylacetonate (Acac)

In general bidentate , bound through both oxygens, but sometim CH3-C(O)es bound monoani bidentat CH2-C(O)through onic e CH3 the central carbon only, see also analogou s ketimine analogue s compoun ds with a C-C double bond and other arenes bidentat e

Alkenes

R2C=CR2

neutral

Benzene

C6H6

neutral

1,2Ph2PC2H4P neutral Bis(diphenylphosphino)eth Ph2

ane(dppe) Can bond to 2 metal atoms at once, forming dimers tetradent ate primarily for alkali and alkaline earth metal cations primarily for alkali and hexaden alkaline tate earth metal cations neutral Althoug h monoani onic, by the nature of its occupied MO's, it is capable of acting as a tridentat e ligand.

1,1Bis(diphenylphosphino)me C25H22P2 thane(dppm)

neutral

Corroles

Crown ethers

neutral

2,2,2-crypt

Cryptates

Cyclopentadienyl (Cp)

[C5H5]

monoani onic

Diethylenetriamine (dien)

C4H13N3

neutral

related to TACN, but not tridentat constrain e ed to facial complex ation

Dimethylglyoximate (dmg H) (HOOCCH2)2NEthylenediaminetetraacetat (CH2)2e(EDTA) N(CH2COOH)2 Ethylenediaminetriacetate (HOOCCH2)2N(CH2)2-O(CH2)2-O(CH2)2N(CH2COOH)2

monoani onic tetraanionic actual hexaden ligand is tate the tetraanion

actual trianioni pentade ligand is c ntate the trianion

Ethyleneglycolbis(oxyethylenenitrilo)tetraacetate (EGTA)

tetraanionic

octodent ate

glycinate (Glycinato)

other amino acid monoani bidentat anions onic e are compara ble (but chiral) macrocy dianioni tetradent clic c ate ligand NO+ cationic bent (1e) and linear

Heme

Nitrosyl

(3e) bonding mode Oxo O dianion sometim monode es ntate bridging ditopic tridentat e monoani monode ambident onic ntate ate neutral meridion tridentat al e bonding only macrocy clic ligand see also tridentat the e N,N',N"trimethyl ated analogue monode ntate tetradent ate monode ntate monode ntate tetradent ate tetradent ate sometim es bridging

Pyrazine Scorpionate ligand Sulfite 2,2',5',2Terpyridine (terpy)

N2C4H4

neutral

Triazacyclononane (tacn)

(C2H4)3(N R)3

neutral

Tricyclohexylphosphine Triethylenetetramine (trien ) Trimethylphosphine Tri(o-tolyl)phosphine Tris(2aminoethyl)amine (tren) Tris(2diphenylphosphineethyl)a

(C6H11)3P or (PCy3)

neutral neutral

PMe3

neutral

P(o-tolyl)3 neutral (NH2CH2C neutral H2)3N neutral

mine (np3) Terpyridine Tropylium Carbon dioxide C15H11N3 C7H7+ CO2 neutral cationic see metal carbon dioxide complex tridentat e

Thus, we have seen that Co-ordination compounds are classified in terms of the central metal M n+, about which a variety of ligands L, L', L" and so on, may be placed in an unlimited number of combinations. The overall charge on the resulting complex [MLx LyLz] is determined by the charge on M and sum of the charges on the Ligands.

The ability of a complex to engage in reactions that result in replacing one or more ligands in its coordination sphere in called its lability. Those complexes for which such substitution reaction are rapid, are called labile whereas those for which such substitution reactions proceed slowly (or not at all) are called inert. It is to be noted that these terms should not be confused with thermodynamic stability and unstability [91]. For example : [Cu(OH2) 6]2+ (aq) + NH3 (aq) instantaneous [Cr(OH2) 6]3+ (aq) + NH3 (aq) several hours As for metal hexa-aquo ions in the first transition series, most are labile. The only two tha are not are Cr(III) and Co(III). And that is why we often start off with a solution of Co(II) when we want to make complexes of Co(III) : Co (II) is labile so we can do rapid substitution reactions on it and then oxidize it pretty easily to Co(III), whereas if we started off with Co(III), which is inert, our substitution reaction would be much slower.

We can measure the rate of these reactions by dissolving a hexa-aquo complex in water labelled with 18O and then monitoring how long it takes for the labelled water to exchange with the unlabelled ones in the inner coordination

sphere. You ought to be aware that for some hexa-aquo ions in the 2nd, and particularly the 3rd transition series, substitution reactions can take a long time thousands of years in some cases ! While were on the subject of hexa-aquo ions, we ought to be aware that they are to some extent acidic. Attaching a water molecule to a metal centre takes some of the electron density from the oxygen and consequently makes the hydrogens easier to pull off as H+. Hence, if you take something like hydrated iron (III) chloride, dissolve it in water, and measure the pH, you will find that it is somewhat acidic.

A practical definition of the terms labile and inert can be given here. Inert complexes are those whose substitution reaction have half life longer than a minute. Such reactions are slow enough to be studied by the classical techniques where the reagents are mixed and changes in absorbances, pH, gas evolution is observed. Labile complexes are those that have half lives for a reaction under a minute. Special techniques are required for collecting data during such reactions, as they may appear to be finished within the time of mixing.

1.3 Kinetics and Mechanism of Ligand substitution reaction.

Two extreme mechanistic possibilities may be considered for any ligand substitution process or for any single step in a series of substitution reaction [92]. First, there is the dissociative (D) mechanism in which the ligand to be replaced dissociates from the metal centre and the vacancy in the co-ordination sphere is taken by the new ligand. (Eqn. 1.1)

(1.1)

Thus, we see that the most important feature of such a mechanism is that the first step (dissociation of the leaving group) is rate determining step, once formed by the cleavage of the bond to the leaving group X, five coordinate intermediate will react with the new ligand Y, almost immediately. The kind of mechanism is synonymous to SN1 mechanism in organic systems, since the formation of the intermediate with reduced co-ordination number is unimolecular as well as rate determining.

The other extreme possibility for ligand substitution is the addition elimination mechanism, or the associative (A) mechanism. In this case the new ligand Y, directly attacks the original complex to form a seven membered intermediate in the rate determining step Eqn. 1.2. After this step, the leaving group X is lost in a fast step. This mechanism can be compared to the SN2 mechanism of organic system, since the rate determining step is bimolecular.

(1.2)

In many substitution reactions, well defined five or seven membered intermediates are not observed, instead the transition state found, has some degree of bond breaking and some degree of bond making, abbreviated as I mechanism i.e. Interchange mechanism [93]. They may be of Ia [94] or Id [95] type as explained below.

In the case of the Ia mechanism we could say that the bond from the incoming ligand starts to form before the leaving one starts to break. In the Id mechanism, we could say that an existing metal-ligand bond starts to lengthen or weaken before the incoming ligand arrives. A pure interchange would have the

leaving ligand-metal bond weaken at the same time that the incoming ligandmetal bond forms. There are three most important type of cases which show some sort of complication present in reaction mechanism. (i) Solvent Intervention (ii) Ion Pair Formation (iii) Conjugate base Formation (i) Solvent Intervention

Many reaction of complexes have been studied in solvents that are themselves ligands. Water, for example is a very good ligand of this category and is present in aqueous solution in high and effectively constant concentration. The substitution of X by Y might take place as under Eqn. 1.3 and 1.4.

MXn + H2O (1.3) MX n-1 H2O + Y (1.4)

MXn-1 H2O + X MXn-1 Y+ H2O

Intervention of solvent like water obscures the molecularity of the rate determining step, the reaction will necessarily be observed to be of first order because of high and constant concentration of the entering ligand, H2O.

(ii)

Ion Pair Formation It occurs when the reacting complex and the entering ligand are both ions, especially when both have high charges Eqn. 1.5. [M X5]n+ + Ym(1.5) {(M X5)Y}n-m

Polycationic complexes tend to form ion pairs with anions and these ion pairs often undergo reactions via the Ia pathway. The electrostatically held nucleophile can exchange positions with a ligand in the first coordination sphere, resulting in net substitution. An illustrative process comes from the anation (reaction with an anion) of chromium (III) hexaaquo complex :

[Cr(H2O)6]3+ + SCN(1.6) {[Cr(H2O)6], NCS}2+ (1.7)

{[Cr(H2O)6], NCS}2+ [Cr(H2O)5NCS]2+ + H2O

When ion pairs are featured as intermediatesin the reaction path that leads to ligand substitution, then the observed rate laws will be of second order, whether or not mechanism at the rate determining step involves, Associative and dissociative Pathways [91, 92].

(iii)

Conjugate base Formation

When experimental rate laws contain [OH-] then there is a question whether OH- actually attacks the metal in a true associative fashion or whether it appears in the rate law through operation of mechanism Eqn. 1.8 and 1.9. [Co (NH3)5Cl]2+ + OH- [Co (NH3)Cl]2+ + Y- (1.9)
+ [Co(NH 3)4 NH2Cl] + H2O OH [Co(NH3)5 Y]2+ + Cl-

fast (1.8) slow

In this conjugate base (CB) mechanism, the rate for the hydrolysis of cobalt (III) ammine halide complexes are deceptive appearing to be associative but proceeding by an alternative pathway. The hydrolysis of [Co(NH3)5 Cl]2+ follows second order kinetics; the rate increases linearly with concentration of hydroxide as well as the starting complex. Based on the information, the reactions would appear to proceed via nucleophilic attack of hydroxide at cobalt. Studies show, however, that in the hydroxide deprotonates one NH3 ligand to give the conjugate base of the starting complex, i.e. [Co(NH3)4 (NH2)Cl]+ . In this monocation, the chloride spontaneously dissociates. This mechanism is compable to the SN1 CB mechanism of organic system.

Water Exchange in Aqua Ions Of the many reactions in which complexes are formed occur in aqueous solution, one of the most fundamental reactions in which the water ligands in the

aqua ion [M(H2O)n] m+ are displaced from the first co-ordination shell by other ligands come under this category. In this, a new ligand is another water molecule, i.e. the water exchange reaction [91]. It is convenient to classify metal ions in four categories based on the measured exchange rates : Class I : Very fast (diffusion controlled); k > 108 s-1 Alkali, larger earth alkaline metals like Cd2+, Hg2+, Cr2+, Cu+ come under this category. Class II : Rate between 104 108 s-1 Divalent first-row transition metals (except V2+, Cr2+, Cu2+) Ti3+, Mg2+, trivalent lanthanides, depict this category. Class III : Rate between 1 104 s-1 Be2+, V2+, Al3+, Ga3+ , show this rate. Class IV : Kinetically inert; rate between 10-6 -10-2 s-1 Ions like, Cr3+, Co3+, Rh3+, Ru2+, Ir3+, Pt2+ , belong to this category.

Many other reviews on the substitution reactions involving specific metal ions viz. Ni (II) [96], Fe III [97], Cd [98], Pd(II) [99] have been attempted by previous investigators. Therefore, only a brief description based on the following broad heading will be presented.

1.4 Formation Reaction The formation of metal complexes take place in media where usually water acts as a solvent. The rate of there reactions vary from very slowly to very fast. The generally accepted mechanism for complex formation was originally proposed by Eigen and Tamm [100 - 103]. For complexes of unidendate ligands it involves the formation of an outer sphere complex between solvated metal ion and the incoming ligand followed by loss of a solvent molecule from this outer sphere compelx to give the desired species. The mechanism of formation of complexes of multidentate ligand can be extended to the formation of complexes of multidentate ligands with the minor modification that the ring closure may constitute the rate determining step. The Eigen and Tamm

mechanism on the formation of labile complexes involving divalent cation is, by now, fairly well enstablished [104]. The formation of M(III) complexes in general and Fe(III) in particular have already been described in detail by a review on the subject [105].

1.5 Dissociation Reaction The dissociation of metal complexes can be considered as the reverse of the complex formation. These reactions are, generally much slower than the formation reactions. The mechanism proposed for the complex formation also accounts for the dissociation rates of complexes bearing unidentate, bidentate or ambidentate ligands. In case of complexes of bidentate or ambidentate ligands the rate constant depends upon opening of the chelate ring or sometimes rupture of penultimate metal-ligand bonds. Both these situations have been encountered frequently with outgoing bidentate or multidentate ligand groups. The presence of an acid generally enhances the dissociation rate because of protonation of the released ligand stablises the intermediate relative to the fully coordinated form [106, 107].

1.6 Ligand Exchange Reactions Ligand substitution reactions of coordination compounds have been studied as intensively as any class of inorganic reactions. The kinetics of these processes have been investigated extensively for octahedral and to a lesser extent for square planar complexes. A very wide span of rates is found ranging from the extremely slow exchange of CN- with NiCYDTA2- ( no evidence for the formation of [Ni(CN)4]2- in 60 days) [108] to the almost diffusion controlled exchange of H2O between [Cu(H2O)6]2+ and water (t = 108 sec.) [109]. There are the four types of substitution reaction met with coordination chemistry.

a. b. c. d.

Monodentate ligand displacement reaction (excess ligand) Multidentate ligand displacement reaction (excess ligand) Metal exchange reactions between ligands (excess metal) Double exchange reactions.

The above exchange reactions are often sluggish in nature because the reaction involves the breaking of a series of coordinate bonds in succession. In

case of displacement of the multidentate ligand EDTA, for example six bonds must be broken during exchange process.

1.6.1 a. Monodentate Ligand Displacement Reactions This section is concerned with the kinetic and mechanism of substitution in complexes where monodentate ligands exchange with monodentate or multidentate ligands.

1.6.1a1. Unidentate by Unidentate Ligands The substitution of one unidentate ligand by another is the simplest situation to consider and has been extensivey used for investigating the mechanism of substitution in some octahedral complexes as well as some squareplanar complexes. The general reactions involve the replacement of a monodentate ligand present in the inner coordination sphere in the solvent media.

There are two basic mechanisms for monodentate ligand exchange in aqueous solution. Considering the nickel-hexaamine system the first mechanism would be a dissociate type : r.d.s [Ni (NH3)6]
2+

[Ni (NH3)6]2+ + NH3 +NH3 [Ni (NH3)6]2+ (1.11)

(1.10)

[Ni (NH3)5]2+

The second would be bimolecular mechanism involving water molecules :

r.d.s [Ni (NH3)6] + H2O [Ni (NH3)5H2O]2+ +NH3

2+

[Ni (NH3)5 H2O]2+ + NH3 [Ni (NH3)6]2+ + H2O

(1.12) (1.13)

It is difficult to distinguish between such mechanism in aqueous solution. However, the lack of NH3 attack on [Ni (NH6)5]2+ and the fact that a

change of 30% in H2O concentration produced no observable effect support a dissociative mechanism [110].

The kinetics of substitution reaction of a series of complexes of the type [Ni Fe(CN5) L](3n) have been studies by Toma and Melin [111, 112] where L was an aromatic nitrogen heterocycle and the substitution ligand was Nitroso-R-salt ( N-R-salt). The rate of substitution varied with the nature of L and a saturation kinetic, typical of rate determining loss of L from the complex, followed by rapid addition of the incoming ligand was reported. This is the first study [114] about monodentate ligand substitution reactions of simple low-spin Fe(II) complexes which generally proceed by D or SN1 (lim) mechanism according to following scheme (Eqn. 1.14).

Fe(CN5) L]

(3-m)-

kLd kL

[Fe(CN5)]3 +Lm kL1 + Ln1 (1.14)

Fe(CN5) L1](3n) Where m and n are charges on L and L1 respectively. A similar study [115] of the reaction of [Fe (CN)5SO3]5 with CN- has also been reported. Other examples include aquation of [Fe (CN)5NO]2 [116] and its reaction with ammonia hydroxylamine or hydrazine [112]; the reaction of [Fe (CN)5(3,5 Me2-Py)]3 [117]with CN- Pyrazine ( Pz) and imidazole ( Imid H) [118], the reaction of [Fe (CN)5 PhNO]3 [119], of [Fe (CN)5SO3]5 [120], of [Fe (CN)5Py]3 [121]with cyanide ion. The photochemical reaction of [Fe(CN)5NO]2- with thiourea [122] or diethylethiourea in methanol have also been study and shown to follow second order rate law [123]. Several reports have appeared on the complex formation reactions involving [Fe(CN)5H2O]3- . The tendency of this ion to dimerise at higher concentration and the nature of the dimeric species [124 , 125] involved have also been discussed. The rate data of some work on the formation and dissociation reactions of [Fe(CN)5L](3-m)complexes have been compiled from literature and are given in Table 1.1. Kinetic and thermodynamic data from mechanistic studies are consistent with a dissociative 'D' mechanism involving the five coodinated intermedia [Fe(CN)5]3is likely for most of these reactions although some researchers still favour on Id mechanism [126, 127].

Recently Abu Gharib et al. [113] have reported the kinetic data for the reaction of [Fe (CN)5(4-CN-Py)]3 with a variety of incoming ligands over a range of concentration in order to provide a good illustration of the saturation kinetics. Together with respective double reciprocal plots. These authors claim that hese results are compatible with a limiting dissociative mechanism.

Malin and co-workers [128] have observed that the intermediate [Fe [Fe(CN)5]3 is quite insentive to the nature and charge of the attacking reagent. In order to examine the influence of charges on the attacking reagents. Bradic et al. [129] studies the kinetics of replacement with L1n. A being PhNO, 3-CN-Py,

DMNA, SCN-, CN- and SO32- , and the leaving ligand Lm being DMNA, PhNO, SO32- and H2O respectively. Finally, they concluded that the magnitudes of second order rate constant kL1 are similar and vary with Ln a in the range of approximate 200-300 M-1s-1 , 42 to 60 M-1s-1 and 33 M-1s-1 for uncharged molecule, uninegative ion and SO32- respectively. The effect of ionic strength fits fairly well with the Bronsted -Bjerrum equation [129]. Limiting reaction rates, at sufficiently large concentrations of entering ligand L1n have been observed with all leaving ligands, except water where the replacement obey a second order rate law [112, 128, 129] as given in Eqn. 1.15. (1.15)

Table 1.5 Kinetic and activation parameters at 298o K for the formation and dissociation of various pentacyano (ligand) ferrate (II) compelexes KfM1 -1 s 1 2 Pyridine 365 4-Methylpyridine Isonicotinamide 296 4-Picoline 354 Pyrazine 380 n-Metylpyrazinium 550 Dimethylsulphoxide 240 4,4 bipyridine Thiourea 286 Allylthiourea 196 Dimethylthiourea 238 Glycinate 28.0 Imidazole 240 N'-Histidine 320 3 N -Histidine 320 Cyanide 38 Thiocyanate 64 3-Cyanopyridine 370 Nitrile 42 DMN Aniline Ligand Kd x 104,s-1 3 11.0 11.5 7.3 4.2 2.8 0.75 6.2 390.0 451.0 813.0 26.7 13.3 5.3 1090 12.0 Ca0.20
H (kJ mol-1) 4 103.7 (67.3)* 100.3 108.7 (66.0) - (63.1) 110.3 (64.4) 114.9 (70.2) 110.8 (64.4) 110.8 69.4 (65.6) 68.1 (69.8) 75.2 (64.8) 97.0 (61.5) 101.6 (63.5) 105.3 (64.4) 91.1 (644) S (JK-1 mol-1) 5 46.0 (29.3)* 37.6 58.5 (25.1) - (16.7) 58.5 (20.9) 74.6 (41.8) 46.0 (16.7) 66.9 -37.6 (20.9) -41.8 (33.4) -12.5 (16.7) 29.2 (-12.5) 41.8 (12.5) 46.0 (20.9) 41.8 (20.9) -

Ref. 6 111, 128 111 111, 128 128 111 111 128 111 125 125 125 126 126 126 126 129 129 129 129 129 127

Cyclohexylamine Ethanolamine

13.56 7.72

96.5 97.8

46.0 127 38.0 127 Continued on page no. 16

Table 1.1 (continued) 1 2 3 4 5 6 Morpholine 7.16 103.2 53.9 127 NH3 190 12.0 102.4 63.1 127 MeNH2 130 4.46 103.2 53.9 127 MeNH 80 7.79 100.3 49.7 127 Me3N 60 12.2 91.4 28.8 127 n Bu NH2 250 7.47 105.7 66.9 127 EtNH2 180 7.54 104.1 38.0 127 n Pi NH2 200 7.38 107.0 71.0 127 Bipyridine 8.43 94.9 29.0 127 En 330 51.5 97.0 37.7 130 enH+ 620 104.0 99.90 50.1 130 Sulphite 0.57 Ca 119.5 Ca 75.2 130 Nitrosobenzene 0.016 Ca 117.0 Ca 41.8 130 N-Methylimidazole 418 32.4 81.5 131 Isonicotinohydrazide 325 7.3 107.8 59.8 132 Pd 54.0 100.5 58.7 133 + pdH 83.0 100.5 53.7 133 bd 46.0 102.4 58.7 133 + bdH 69.0 104.5 62.7 133 Ptd 45.0 103.7 58.7 133 ptdH+ 64.0 101.6 53.7 133 hxd 41.0 100.5 45.8 133 hxdH+ 53.0 96.5 37.8 133 1,4-Tx 5.71 112 71 134 1,4-DT 5.58 105 44 134 1,3-DT 3.39 108 50 134 * Numbers in parenthesis give the values of H and S for the formation reactions.

In recent years one of the diagnostic tests that is being widely applied # for elucidating the substitution mechanisms, is the volume of activation (V ) [135-137]. Thus, the most convincing evidence in favour of D mechanism comes # from the determination of V . If the leaving group of D mechanism comes from # the determination of V . If the leaving group Lm is to dissociate completely in # the transition state then a positive value of V is interpreted as representating a

stretching of a metal-ligand bond in the transition state and this favours a D mechanism. Activation volumes [118] for ligand substitution reaction on several pentacyano (ligand) ferrate (II) complexes by few incoming ligands are isted in Table 1.6. The values listed in Table 1.6 are all the positive values.This suggests that either a dissociative mechanism or a mechanism involving charge dispersal in the transition state is obeyed [146].

In the D mechanism of the scheme given in Eqn. 1.5 there is a competition between incoming ligand Ln1 and the outgoing Lm for the transient intermediate [Fe(CN)5]3- produced from [Fe(CN)5 L] (3- m)- which is characterized by the ratio of the second order rate constant kL1 / KL. This gives an idea of the reactivities of a variety of ligands for the intermediate [Fe(CN)5]3-. Reactivity ratio for various nucleophiles in aqueous solution are listed in Table 1.3. Solvent effects on relative reactivities of [Fe(CN)5]3- in various binary aqueous mixtures have also been discussed [147].

Table 1.6 Activation volumes ( V#) for some ligand substitution reactions on pentacyano (ligand) ferrate (II) complexes by various incoming ligands in aqueous and nonaqueous medium. Reaction 1 3Fe(CN)5L +CN Fe(CN)64- +L L = 4-(1-butylpentyl) pyridine L=4-phenylpyridine L=N-)n-pentyl)pyrazinium (Na2salt) L= Pyrazine Fe(CN)5L3-+CN- Fe(CN)64- +L L=4-CNpy L=4,4' - bpy L=4-t Bupy Fe(CN)5L3-+CN- Fe(CN)64- +L L = p- (CH3CH2CH2)CHC5H4N L=p-(C5H4N)2 L=p-(C6H5)(C5H4N) L=p-CH3(CH2)5NC4H4N+ L=p-C6H4N2C2H2 Solvent 2 H2OMeOH H2O H2O H2O H2O H2O H2O 20% MeOH H2O H2O H2O H2O +16 +10 +10 +13 +19.0 0.5 +13.5 0.7 +11.4 1.0 +16.3 1.4 +13.6 0.5 +10.4 0.5 +9.6 0.8 139 V# (cm3mol-1) 3 Ref. 4 138

140

L=p-(CH3)3CC5H4N L=p-NCC5H4N L=p-CH3CC4H4N2+ L=p-C4H4N2 L=p-CH3C4H4N2+ Fe(CN)5(4-CNpy)3-+CN- Fe(CN)64- +4CNpy Fe(CN)5(NH2R)3-+py Fe(CN)5(py)3- + NH2R R=H R=CH3 R=C2H5 R=PhCH2 R=1Pr Fe(CN)5H2O3-+Ln- Fe(CN)5L(3+n)- +H2O Ln- = imidazole Ln- = histidine Ln- = methionine Ln- = glutathione Ln- = glycine Ln- = -alanine Fe(CN)5H2O2-+L L = cytosine L = cytidine L= CMP Fe(CN)5L2- +H2O

H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O

+17.9 0.4 +11.4 1.0 +19.0 1.0 +0.9 0.5 +12.5 1.2 +20.9 0.5 +19.0 1.0 +16.4 +24.0 +16.3 +17.4 +18.5 +15.5 +17.0 +17.9 +14.1 +16.4 +16.8 0.6 1.0 1.5 1.4 0.6 0.7 0.4 0.6 0.4 0.6 0.2

141 142

143

+2.5 0.5 +9.5 1.2 +12.8 1.1 +20.1 1.0

144

Fe(CN)5(NO2)24-+H2O Fe(CN)5(H2O)3-+NO2-

145

Table 1.7 Reactivity ratios KL1/KL for the replacement of a lignd Lm by an incoming ligand Ln1 in the omplexes of the type [Fe(CN)5-L](3-m)- in aqueous solution at 250C

Outgoing ligand Lm 4-CN-Py 3-CN-Py p-Me2NC6H4NO p-Me2NC6H4NO SO32-

Incoming ligand Ln1 CNCNCNPhNO CN-

Ratio of rates KL1/KL 0.03 0.05 0.10 0.80 9.0

Ref. 147 147 129 129 115

H2O

CN-

12000

119

1.6.1 a2 . Multideatable By Unidentate The exchange of multidendate ligands by unidendate ligands is another example of unidendate ligands exchange reactions.

Recently Nigam and coworkers have investigated the kinetics and mechanims for replacement of aminocarboxylates from mono (aminocarboxylato) hydroxoferrate (III) complexes by cyanide ions [148 - 150]. The general mechanistic scheme for [NiL](2-n)-CN- replacement reactions requires that three cyanides are bonded to Nickel (II) ion while four cyanides are required in [Fe L(OH)](2-n)-CN- systems (n= charge on ligand L) in their respective rate determining step. The last cyanide adds rapidly forming [Ni(CN)4]2- or [Fe(CN)5OH]3- as the case may be. Some bis [151-152] and binuclear [153-155] nickel (II) complexes of multidentate ligands react with cyanide ion by a cyanide independent dissociative path (Eqn. 1.16, 1.19) and cyanide dependent associative path (1.17, 1.18, 1.20, 1.21) Bis NiL2 NiL2 + CNNiL(CN)+3CNkd NiL + L NiL (CN) + L NiL (CN)42- + L ( in steps) NiL + Ni2+(aq) NiL (CN) + Ni2+(aq) NiL (CN)42- + L ( in steps) (1.16) (1.17) (1.18)

Binuclear

Ni2L Ni2L + CN-

kd

(1.19) (1.20) (1.21)

NiL(CN)+3CN-

The [FeL(OH)](2-n)-CN- reaction presents some complications and takes place in three distinct stages [148-150]. The mechanism for the first stage i.e. the formation of [Fe(CN)5(OH)]3- from [FeL(OH)](2-n) complexes as already been reported for many aminocarboxylates as hown in eqn. 1.22-1.26

[FeL(OH)]

(2-n)

+ CN

K1 K2 K3 k4 k-4 k5

[FeL (OH)(CN)](1-n) fast [FeL (OH)(CN)2]n- fast [FeL (OH)(CN)3] (n+1)- fast

(1.22) (1.23) (1.24)

[FeL(OH)(CN)](1-n) + CN[FeL(OH)(CN)2]n- + CN[FeL(OH)(CN)3](n+1)- +CN[FeL(OH)(CN)4](n+2)- +CN-

[FeL (OH)(CN)4] (n+2)- r.d.s. (1.25) [Fe(CN)5(OH)]3 + Ln- fast (1.26)

Where L = HPDTA4-, HIDA2-, EDTA4-, HEDTA3-, DTPA5-, PDTA4-, and TTH A .The second stage of reaction is the conversion of [Fe(CN)5 OH]3- to [Fe(CN)6 ]3- due to reaction with cyanide ions, present in excess according to Eqn. 1.27
63[Fe(CN)5 OH]3- +CN- [Fe(CN) + OH6]

(1.27)

The third stage involves the oxidation of aminopolycarboxylates released in the first stage Eqn. 1.26 by [Fe(CN)6 ]3- formed in the second stage as shown in Eqn. 1.28
3[Fe(CN)6 ]3- +Ln- [Fe(CN) + oxidation product of Ln- ( 6]

1.28)

The cyanide is a potential unidentate ligand having the capacity of displacing multidentate liands viz. microcyclic ligand, polyamines, polyaminocarboxylates and thioligands from their metal complexes. The reactions involving [NiL](2-n) compelexes ( L = polyaminoarboxylates [108, 156-157] and polyamines [158 - 159] microcyclic ligands [160, 161]) with cyanide ions have been studied extensively by many workers.

1.6.1 a3. Unidentate by Multidentate

This type of reactions have been studied extensively in connection with the replacement of coordinated water during the formation reactions of multidentate ligand complexes [162]. The reactions of open chain and macrocyclic polyamines with Cu(II) in strongly basic solutions have been studied [163] to examine the kinetic behavior of the unprotonated ligands. Some kinetic information is also available on the reactions of [Ni(CN)4]2- with aminopolycarboxylate ligands. A mixed [Ni(CN)3 L](n+1)- complex is formed before the rate determining step in which an additional CN- is lost. The behavior with trien is different, however, becaue the rate-determining step is the reaction of the ligand directly with [Ni(CN)4]2- by an associative mechanism [164]. Also the disappearance of [Ni(CN)4]2- is greatly accelerated by the polyamine concentration in comparison to the much slower reaction of [Ni(CN)4]2- with aminocaboxylates [108, 156]. Margerum et al. [114] have reported the reaction of [Ni(CN)4]2- with a few polyamines in presence and absence of I2 as a scavenger for cyanide ion. In presence of I2 the released cyanide has no effect on the forward reaction rate but in absence of I2 there is an inverse effect. 1.6.2 Multidentate ligand displacement reactions

The mechanisms by which one multidentate ligand displaces another from a metal ion depends upon the ability of both ligands to coordinate with the metal ion simultaneously. There are four accepted mechanisms for this type of reactions.

(i)

The outgoing ligand (L-L) is completely dissociated from the metal cation (M) before association between M and the incoming ligand (L-L)* starts.

(1.29)

(1.30)

(ii)

The association of the metal cation with the incoming ligand may begin before dissociation of the outgoing ligand is complete. In this mechanism there will be an intermediate, in which both ligands are bonded to the same cation.

(iii)

(1.31) A variation on the above mechanism in the case of pre equilibrium partial dissociation of he starting complex.

(1.32 )

(iv)

In the last scheme, there is a modification of the previous scheme, one which can apply when two multidentate e.g., tetradentate ligands are replaced by another multidentate e.g. quinqui of hexadentate ligand.

(1 .33)

The rate determining step of overall reaction is the cleavage of any one of the several bonds between metal and the leaving group which must be broken in the course of the reaction. As example, Ni Tet2+ reacts with EDTA [165], TMDTA [166], PDTA or DTPA [167] and Nitrien2+ reacts rapidly with EDTA [168], HEDTA[169] or DTP [170] forming mixed ligand intermediates and give respective products by unwrapping of Tet or Trien.

A review of on multidentate ligand exchange reaction and their application to analytical chemistry has appeared for system involving EGTA and 4(2-Pyridylazo) resorcinol [171]. Other multidentate ligand exchange reactions of metal ions such as Cu(II) [172-174], Zn (II) [175], Hg (II) [176], Cd (II) [177179] and Ni (II) [180-184] have been investigated by many workers.

The elucidation of substitution mechanism of a coordinated ligand to Fe(III) centre by another incoming ligand has been the subject of considerable interest for many workers [185-189], including some other scientists [150]. Most of these studies are largely centred around exchange of a polydentate by a monodentate or monodentate by polydentate ligand. On the contrary, there have been limited reports on the kinetic and mechanistic studies involving the exchange ofa polydentate ligand coordinated to Fe(III) by another polydentate ligand [190-192].

We have recently investigated the kinetics and mechanism of the exchange of HIDA coordinated to Fe(III) viz. from [Fe HIDA (OH2)]- by Par (2Pyraylazo resorcinol). This reaction seen to proceed through the following mechansitic scheme Eqn. 1.34-1.36.

[FeL(OH) + HR [RFeL]2

k1 [RFeL]2 +H2O k-1 k2 k-2 [FeR]* +L3fast (1.34)

r.d.s.

(1.35)

[FeR]

k3 k-3

[FeR2] + H+

fast

(1.36)

This mechanism is in confirmation with the mechanism proposed earlier by Nigam et al. [191] and us [192] for FeL-Par (L = HEDTA and NTA). Mentasti et.al. [190] has investigated the kinetics of displacement of metallochromic indicators (In) from their complexes of Fe(III), represented by the Eqn. 1.37.

Fe In + EDTA

Fe EDTA + In

(1.37)

In = Salicyclic acid H2S4I or Tiron = 1, 2-di hydroxy benezene disulphonic acid (H2T). In many multidentate ligand replacement reactions the rate expression contains terms in various powers of the hydrogen concentration, which arise from the possible ways of protonating the ligands both free and in complexed form. It has been possible to resolve the rate constants due to various protonated reactant by algebraic manipulation and mathematical analysis of reaction rates measured over a wide pH range and resorting to some simplifying assumptions about species distribution.

1.6.3

Metal Exchange and Displacement Reactions

The displacement of one metal cation from its complex, with a multidentate ligand by another metal ion (or the exchange with an identical labelled metal ion) is represented by Eqn. 1.38. M + M'L M' + ML (1.38)

Mechanism of metal displacement can be either dissociative

(1.39)

or associative in nature.

(1.40)

The mechanism of some metal cation displacement reactions are indicated in Table 1. 8

Table 1.8 Mechanism of some cation displacement reactions from Multidentate Ligand Complex Complex Ca (II)-TTHA Cd (III)-CYDTA Cd (III)-EDTA Cd (II)-(EDTA)HCu (II)-EDTA Fe (III)-HEDTA, -DTPA Fe (III)-HEDTA, -EGTA, DTPA [Fe(III) (EDTA) H2O][MEDTA]- (m=Gaor In) Bi (III) EDTA Replacing cation M(II) (M-Co, Ni, Cu, Zn) Cu(II) Cu(II) Cu(II) Cu(II) Cd(II) Ga(III) In (III) Fe (III) Fe (II) Type of mechanism DA D DA DA DA D D D D Ref. 193 194 195 196 197 198 199 200 201 202

Reactions following Eqn. 1.39 are represented by D and Eqn. 1.40 by DA.

1.6.4

Double Exchange Reactions

An interesting situation exists when two multidentate complexes are mixed and thermodynamics dictates a double exchange reactions [203]. The exchange of ligands of the type given in Eqn. 1.41 between two metal ion chelates has been studied [204-206] and was found to be a slow process if the reaction goes via a dissociation sequence.

ML + M'L' (1.41)

M'L + ML'

No evidence for the formation of a dicomplex intermediate has been given so far, but the rates of such coordination change reaction were found to increase enormously if small amounts of either ligand or metal ion is added [207-209] to

the reaction mixture. This increase is the consequence of a coordination change mechanism

1.7

Electron transfer Reaction

Electron transfer (ET) occurs when an electron moves from an atom or a chemical species (e.g. a molecule) to another atom or chemical species. ET is a mechanistic description of the thermodynamic concept of redox, wherein the oxidation states of both reaction partners change. Numerous biological processes involve ET reactions. These processes include oxygen binding, photosynthesis, respiration, and detoxification. Additionally, the process of energy transfer can be formalized as a two-electron exchange (two concurrent ET events in opposite directions) in case of small distances between the transferring molecules. ET reactions commonly involve transition metal complexes[210,211] , but there are now many examples of ET in organic chemistry There are several classes of electron transfer, defined by the state of the two redox centers and their connectivity 1.7.1 Inner-sphere electron transfer In inner-sphere ET, the two redox centers are covalently linked during the ET. This bridge can be permanent, in which case the electron transfer event is termed intramolecular electron transfer. More commonly, however, the covalent linkage is transitory, forming just prior to the ET and then disconnecting following the ET event. In such cases, the electron transfer is termed intermolecular electron transfer. A famous example of an inner sphere ET process that proceeds via a transitory bridged intermediate is the reduction of [CoCl(NH3)5]2+by [Cr(H2O)6]2+. In this case the chloride ligand is the bridging ligand that covalently connects the redox partners. 1.7.2 Outer-sphere electron transfer In outer-sphere ET reactions, the participating redox centers are not linked via any bridge during the ET event. Instead, the electron "hops" through space from the reducing center to the acceptor. Outer sphere electron transfer can occur between different chemical species or between identical chemical species that differ only in their oxidation state. The later process is termed self-exchange. As an example, self-exchange describes the degenerate reaction between permanganate and its one-electron reduced relative manganate: [MnO4]- + [Mn*O4]2- [MnO4]2- + [Mn*O4]-

In general, if electron transfer is faster than ligand substitution, the reaction will follow the outer-sphere electron transfer. Often occurs when one/both reactants are inert or if there is no suitable bridging ligand. A key concept of Marcus theory is that the rates of such self-exchange reactions are mathematically related to the rates of "cross reactions". Cross reactions entail partners that differ by more than their oxidation states. One example (of many thousands) is the reduction of permanganate by iodide to form iodine and, again, manganate. Five steps of an outer sphere reaction 1. reactants diffuse together out of their solvent shells => precursor complex (requires work =wr) 2. changing bond lengths, reorganize solvent => activated complex 3. Electron transfer 4. Relaxation of bond lengths, solvent molecules => successor complex 5. Diffusion of products (requires work=wp) 1.7.3 Heterogeneous electron transfer In heterogeneous electron transfer, an electron moves between a chemical species and a solid-state electrode. Theories addressing heterogeneous electron transfer have applications in electrochemistry and the design of solar cells. The first generally accepted theory of ET was developed by Rudolph A. Marcus to address outer-sphere electron transfer and was based on a transition-state theory approach. The Marcus theory of electron transfer was then extended to include inner-sphere electron transfer by Noel Hush and Marcus. The resultant theory, called Marcus-Hush theory, has guided most discussions of electron transfer ever since. Both theories are, however, semiclassical in nature, although they have been extended to fully quantum mechanicaltreatments by Joshua Jortner, Alexender M. Kuznetsov, and others proceeding from Fermi's Golden Rule and following earlier work innonradiative transitions. Furthermore, theories have been put forward to take into account the effects of vibronic coupling on electron transfer; in particular, the PKS theory of electron transfer[212] . Before 1991, ET in metalloproteins was thought to affect primarily the diffuse, averaged properties of the non-metal atoms forming an insulated barrier between the metals, but Beratan, Betts and Onuchic[213] subsequently showed that the ET rates are governed by the bond structures of the proteins -- that the electrons, in effect, tunnel through the bonds comprising the chain structure of the proteins. .

REVIEW PART-II

1.8 Kinetic Catalytic Methods (KCM) of Analysis : Characterization, Classification and Methodology

The bulk of analytical chemistry is based on chemical reactions at metal ion centres in liquid media, particularly in aqueous solutions. Their study, understanding and applications constitute a large portion of todays tasks of analytical chemists. The use of Kinetics by analytical chemists has increased tremendously during the past few years. Reaction rate techniques have been used in the development of analytical methods for estimation of inorganic and organic compounds present in industrial enviromental and biological sample. A brief survey of the significant developments made in this field will be presented here though the discussion will be mainly centred around the recent advances in the applications of ligand substitution kinetics to the determination/analysis of component, in mixtures of catalytic species present in or added to suitable reaction system.

1.9 Classification of Kinetic Methods based on the Chemistry of the Reactions Employed Generally, kinetic method are classified into two broad categories : 1. Methods based on catalysed reaction. 2. Methods base on uncatalysed reaction. Here, methods only based on catalyzed reactions will be discussed.

1.9.1a. Methods based on catalysed (Non-enzymatic) Reactions

These continue to be the most popular methods in the literature of kinetic methods of determination. Their popularity is reflected in Fig. 1.1 which illustrates the growth of the catalytic determination through the years, with information derived from the reviews in the journal, analytical chemistry. Commonly, catalysed reaction are used for the determination of the catalyst(s) and seldom for the reactant(s). The recent development of catalytic methods of analysis/determination is a result of their high sensitivity combined with relatively

simple procedures. A variety of catalytic effects on reactions have been employed in analytical determinations. Catalytic determinations can be broadly viewed as: A. B. Use of primary catalytic rates (determination of catalyst) and Use of modified catalytic rates (determination of modifiers)

1.9.1 a1 . Kinetic Methods Based on Primary Catalytic Effects Two facts must be accounted for catalytic determination : (a) The uncatalysed reaction proceeds simultaneously with the catalysed reaction and (b) The rate of catalysed reaction is proportional to the concentration of the catalyst. The latter is a consequence of cyclic regeneration of the catalyst so that its concentration remains constant. Another practical requirement for successful applications is that the concentration of reactants other than the catalyst or the species, whose changes in concentration is monitored, must be such as to make the reaction rate pseudo-zero order. The species whose change in concentration is being monitored is adjusted to give first order dependence. Thus, for the generalized reaction :

(1.41)

Where S (monitored species) and R are reactants. P and Y are products and C is the catalyst, the general rate expression can be written as :

(1.42) Here kc and ku are the rate coefficients containing some concentration terms for catalysed and uncatalysed reactions respectively and is the initial concentration of the catalyst in the reaction system.

Focussing our attention on the term for the catalysed path in equation (1.27) and accounting for the presence of the catalytic cycle, one can use a simplified two-step reaction scheme as represented by Eqn. 1.43 and 1.44

(1.43)

(1.44)

Depending upon the relative magnitudes of rate coefficients for reactions shown in Eqn. 1.43 and 1.44 two situations may arise :

(a) Pre-equilibrium case and (b) a steady state situation. After resorting to some valid approximations both these conditions demonstrate the proportionality between catalyst concentration and the rate of reaction as given by Eqn. 1.45 [60]

(1.45)

Where k'2 is a composite rate constant made up of some rate constants and concentration terms.

Thus, under stipulated conditions and also recognizing that the uncatalysed reaction is invariably taking place, Eq. 1.42 can be written in a general form for both the above conditions as :

(1.46) Where F[C]0 is a linear function of the catalyst concentration and F is the rate due to uncatalysed path. Eq. 1.45 can be used to determine the concentration of catalyst C using either a differential or an integral approach.

1.10 Methods of MEASUREMENT OF REACTION RATES 1.10.1 Differential Methods 1.10.1a. Initial rate method:

Fig. 1.4 illustrates how the initial rate method is used to determine the concentration of analyte from the experimental rate measurements. Solid curves are the plots of experimentally measured product concentration as a function of time for four standard solutions of analyte (A). Tangents are drawn to each of the curves at a time near zero (dashed lines). The slopes of the tangents/reaction rates are then plotted as a function of analyte concentration giving a straight line. Unknowns are treated in the same way and their concentrations are determined from the calibration graph. (

The initial rate is linearly related to concentration whether the initial portion of the kinetic curve is linear or not, provided that all the measurements are made at the same time interval for different concentrations. Hence it is also called as single point method. The following are the advantages of this method:

1. Since only a small portion of the plot is utilized for measuring the slope, a few data points are enough to make the plot and there is no need to follow the reaction for a long time or to the end. In this way time is saved and the entire procedure is simplified. 2. The reaction obeys pseudo zero order kinetics as the change in the concentration of reactants are very small or negligible. 3. As the amount of product formed is small, the reverse reaction virtually does not take place. 4. Complication arising from possible side reactions is avoided. 5. The reaction takes place at a faster rate at the start of the reaction and results better signals. 6. Useful for reactions whose rate constants are too small to be used in equilibrium methods. The shortcoming of the method lies in accurate measurement of the initial slope. This is overcome by the use of microcomputers or more sophisticated data handling procedures and numerical analysis which provide the slope of the curve directly and precisely. The initial rate method requires the plotting of kinetic curves, certain times it is preferable to use fixed time or variable time methods which do not require the plot of kinetic curves. 1.10.1b Fixed time method In this method, the concentration of reaction product is measured at a predetermined time from the start of the reaction (to t1 = _t). Since _t is kept constant, the concentration of product is directly proportional to the change in the concentration of indicator reaction product (P). By plotting P vs. concentration, you will obtain a straight line with zero intercept as indicated in Fig. 1.5.

Fig. 1.5: As _ t is kept constant, plot of _ P vs concentration will give straight line with zero intercept. Normally _t is chosen from the start of the reaction. However _t can be for tl t2 or t2 t3 provided it is not too far from the start of the reaction and falls within the straight line portion of the kinetic curve. _t is proportional to concentration even in the case of reverse reaction and it is practically superior for pseudo first order reactions. 1.9.1cVariable time method: In this method the time required for the pre-determined change in the solution (absorbance) or the formation of product is measured for a series of analyte concentrations, i.e., _P = constant and measured at times, t1, t2, t3, etc. The application of this method is illustrated in Fig. 1.6

Fig. 1.6 The plot of reciprocal of time, 1/_t vs. concentration The plot of reciprocal of time, 1/_t vs. concentration constitute the calibration graph (Fig. 1.6). This method is more limited than the fixed time method as the _t does not start from t1 = 0.

1.10.2 Integration Methods The experimental procedure is similar to that of differential methods, but the values are integrated over a range and the integrated values are plotted for the tangent, fixed time and variable time methods. In the tangent method, the formation of product is integrated over a finite time interval _t = (t1 t2). Log [P] or log[A]o - [P] is plotted as function of time. This results a series of straight line with positive or negative slopes from which the calibration graph can be constructed. This is illustrated in Fig. 1.7.

Fig. 1.7 log [P] is plotted as a function of time In the fixed time method _(ln[A]) vs. [C]0 for a fixed concentration of A, [A]o constitute the calibration graph. Plot of 1/_t vs. C0 for a series of standards constitute the calibration graph for the variable-time method.

Integration methods are applied to conditions where the reaction proceeds to a greater extent.

1.10.3 Induction Period Measurements This phenomenon was first observed by Landolt in the reaction between iodate and sulphite in an acid medium and called as Landolt effect.

1.47

1.48 The slow reaction is linked to the fast reaction process through the product (P) of slow reaction. Since the second reaction is faster than the first, the product can be detected only when the Landolt reagent/catalyst(L) disappeared completely. The time elapsed till the appearance of product (P) is a measure of catalyst concentration, which is directly related to the induction period (t). The experimental procedure involves the measurement of time elapsed between the addition of the last reactant (either A or B or catalyst) which starts the slow reaction and the first appearance of the signal corresponding to the product. Very low concentrations of catalysts, in the range of microgram and below can be detected by this method. 1.9.4 Differential Reaction Rate Methods An important application of kinetic methods is the determination of closely related species in mixtures such as alkaline earth cations and organic compounds with same functional groups. For example consider the two species A and B to react with a common excess reagent R to form products under pseudo-first order conditions,

1.49 1.50

If they are of first order kinetics, [R]o >> [A]o and [R]o >> [B]o the sum of concentrations of the species at time t is given by

1.51 Ct = [A]t + [B]t = [P] - [P]t = [A]o exp(-kAt) + [B]o exp(-kBt) ... (6.6) and the sum of concentrations of product is given by [P]t = [A]o - [A]t + [B]o - [B]t = [A]o [1- exp(-kAt)] + [B]o [1exp(-kBt)] (6.7)1.52 It is assumed that no product is formed at the beginning. If kA > kB then A is reacted before B. Thus if kA/kB is greater than about 500, about 99% of A is consumed before 1% of B is used up. If the measurement is made shortly after mixing it is possible to determine A with no significant interference from B by differential determination. When the ratio of the two rate constants is small, determination of both species is still possible. Thus by making suitable changes in the reaction conditions such as change of solvent, temperature, concentration or use of masking agent, so that the k values differ considerably and make the measurements possible. 1.9.5 Logarithmic Extrapolation Method Logarithmic extrapolation method is most frequently used in differential kinetic methods of analysis. For first order reaction, log Ct or log ([P] - [P]t) is plotted as a function of time (Fig. 1.8) which results a curve. If kA is larger than kB the species A reacts at a higher rate than B. After time t, [A]t tends to zero and the curve becomes linear, so that log Ct = log[P] - [P]t = log[B]o - kBt/2.303 (1.53) The extrapolation of the linear portion of the curve that causes the intercept corresponds to the initial concentration of B, [B]o. The concentration [A]o is obtained by difference from [P].

Fig.

Logarithmic extrapolation method for a mixture of species. For second order reaction, log[A]t or log[B]t is plotted as a function of time (Fig. 1.9). Line 1 corresponds to faster reaction while line 2 corresponds to slower reaction. The values of [A]o and [B]o can be arrived at from the plot.

1.10.6 Linear Extrapolation Method For first order kinetics and when kA is larger than kB , [P]t is plotted as a function ofboth exp(-kAt) and exp(-kBt) and extrapolated to obtain the required data from them.Same concentrations of individual components of A and B and in the mixture are plotted. [A]o _ and [A]o__ correspond to the concentration of A by extrapolating the slower reaction component and faster reaction component respectively. From the slopes and intercepts, the concentrations of A and B can be computed. For second order kinetic reaction, where [R]o = [A]o + [B]o , the product concentration P is plotted as a function of ([R]o P)t which on extrapolation yield [A]o as its slope for the concentration B . The plot of 1/ ([R]o - P) as a function of time and its intercept on extrapolation yield [B]o directly. The rate constant can be derived from its slope. 1.10.7 Proportional Equation Method It is a mathematical approach and widely used in the resolution of closely related reaction rates in a mixture. Rate constant ratio of 4 is quite enough for this method and it does not require the prior knowledge of total concentration, Ctot. In practice, the concentrations Ct are measured at two or more reaction times, t1, t2, .to formulate two similar equations

1.54 1.55

The initial concentrations of A and B are arrived at by solving the simultaneous equations. The only requirement is that the rate constants must be known earlier. The general equation for a binary mixture will be in the form of

where f is a measurable quantity under two different set of conditions and ,

,
1B 2B

k k are empirical proportionality constants obtained under the above set

of conditions.

2 B k are empirical proportionality constants obtained under the above set of conditions.

Differential and integral methods are most frequently used for catalyzed reaction. Detailed descriptions of methods for the determination of catalytically active substances and a discussion of accuracy and precision are given by Mottola [60] and Perez-Bendito and Silva [61].

It is very important to note that the precision of kinetic methods depends on the reliability of the analytical technical technique used to measure the changes in the concentration of a given component (indicator substance) as a function of time.

The overwhelming majority of indicator reactions chosen for catalytic determinations involve redox system. However, sometimes a reaction involving the exchange of ligands in a complex can be catalysed homogeneously by a metal ion provided that the metal ion has an affinity for the leaving ligand and the experimental conditions are so selected that the catalyst can be regenerated. As an illustrated example, the metal ion catalysed replacement of CN- from [Fe(CN)6]4has been used for the determination of small amount of catalyst metal ions. Pavlovic and Asperger [214] found a method for determining as low as 2.7 10-7 M of Hg2+ in biological materials with relative standard error of about 20%. Nigam et al., have determined down to 1 10-7 M of Hg2+ using p- NDA [215] and Mpz+ [163] as the entering ligand. Table 1.5 gives a summary of analytical applications of catalysed ligand substitution reaction of [Fe(CN)6]4- and [Fe(CN)5NH3]3- . By means of catalytic analytical methods, extremely low levels can be determined at low cost and with a high sensitivity that is equal to that of physical methods of trace analysis. The selectivity of the catalytic determinations, is, however, usually rather lower than that of other methods of trace analysis. The selectivity can sometimes be improved by modification of the indicator reaction through variation of the reagents and their concentrations, or by use of masking reagents or activators, or by combination with a separation method. Modification of the indicator reaction can be exemplified by the selective determination of osmium and ruthenium by their catalysis of the nitrate oxidation of 1-naphthylamine. By

variation of the nitrate concentration and the use of 1,10-phenanthroline and 8hydroxyquinoline as complexing agents it is possible to determine these two elements simultaneously. An especially significant increase in the selectivity is made possible by use of a preliminary separation step. If the ion to be determined is separated by solvent extraction and then catalytically determined directly in the extract, a very specific determination is possible; this technique has been called "extractive catalytic determination". This method has been used for determination of molybdenum (0.5 ng/ml) in sea-water, iron (5 ng/ml) in heavy metal salts, and copper (3 ng/ml) in the presence of numerous elements. Talanta. 1978 Mar;25(3):123-30. Selectivity of catalytic methods of determination. Otto M, Mueller H, Werner G. Table 1.5 Reactions involving exchange on hexacyanoferrate (II) And pentacyano (ligand) ferrate (II) in presence of catalysts Indicator Reaction 1 [Fe(CN)6]4- + PhNO [Fe(CN)6]4- + Bipy [Fe(CN)6]4- + Bipy [Fe(CN)6]4- + PhNO [Fe(CN)6]4- + PhNO2 [Fe(CN)6]4- + Phen [Fe(CN)6]4- + L (in presence of catalyst) [Fe(CN)6]4- + Nitroso-RSalt [Fe(CN)6]4- + Nitroso-RSalt Analyte 2 Hg2+ Ag+, Au3+ Hg2+ Hg2+ Hg2+ Au3+ Phen, Bipy Pd2+, Ag+, Remarks* 3 528nm (2.7 10-7M) pH = 4.1, 20% 520nm(1.6710-6M Ag+, 1.6510-5 M Au3+) 485 nm (1.0 10-5M) 525 nm (0.5 g/2ml) pH=4.1, 7% (10-4M), pH =3.5 (510-5M) , pH =2.4 Ref. 4 161 164

165 166 167 168 169

720 nm (0.04 ppm) 170 pH = 5.05 720 nm (0.05 ppm) 171 pH = 4.0, 5% Continued page no.31

Table 1.5 (Continued) 2 3 2+ + 3+ Hg , Ag , Au 562 nm (0.02 ppm Ag+, 0.1 ppm Au3+, 0.01 ppm Hg2+), pH=4-6, 4.7%, 4.3%, 2.7% respectively [Fe(CN)6]4- + Nitroso-R- Hg2+, Ag+, Au3+ 625 nm (0.01 ppm Salt Hg2+, 0.005 ppm Ag+, 0.05 ppm Au3+), pH=4.5-6.0, 3.75%, 2.15%, 5.44% respectively. Hg2+ 630 nm (1 10-6M) [Fe(CN)6]4- + N N pH=3.5, 6% [Fe(CN)6]4- + p-NDA Hg2+ 640 nm (3.6 10-8M) pH=5.0, 5% [Fe(CN)6]4- + Mpz+ Hg2+ 655 nm (3.6 10-8M) pH=5.0, 1.5% 1 4[Fe(CN)6] + Ferrozine * Detection limit is given in parenthesis and error in %.

4 172

173

174 162 163

Catalysed substitution reaction involving displacement of one-ligand by another in a metal complex have been widely used to determine microgram quantities of catalysts [175]. Tabata and Tanaka have reported kinetic methods for determination of nanogram amounts of Hg2+ [176] and Cd2+ [177] by their catalytic effects on the metal ion incorporation of Mn2+ with , , , - TPPS. Cu2+ catalysed metal-metal exchange reaction of Zn2+ with NiEDTA2- has been exploited by Bydalek and Margerum [178] for determination of Cu2+ at concentration 10-5 M. Double exchange reactions are very sensitive to trace catalysis and inhibition. These properties have led to the development of sensitive analytical methods for concentration down to 10-8 M of metal ion or ligands. [179-181]. Table 1.6 gives an over view of catalytic methods developed for some chemical species using ligand substitution or complex formation reactions.

Table 1.6 Determinations based on catalytic effect of various ions on ligand substitution or complex formation reaction Indicator Reaction 1 ZnII EGTA +Zincon MnII EGTA +PAN ZnII EDTA +NH3 CdII EDTA +NH3 CuII EGTA +PAR HgII CPC + CYDTA CuII H2O+o-Cresol phthalein HgII PAR +CYDTA CrIII (H2O)6 + Xylenolorange CoII (CN)3-5+O2 (coupled to chain coordination) CoII (en)2 salicylate +I2 Analyte 2 Ca2+ Ca2+ Ca2+ Ca2+ Ca2+ NH3 CNICO32O2 Remarks* 3 Polarographic (10-3 M) Polarographic Polarographic Polarographic Spectrophotometric (10-5 M), pH =9 Spectrophotometric (5 10-5 M), pH =9.5, 5% 568 nm (0.25 g/25 ml) pH =11.5 500 nm (10-8M) pH = 8.5 (10-8M), 8% Ref. 4 182 182 183 184 185 186 187 175 188 180

CH3COO- In accetate buffer 189 HCO3 NiII EDTA + Zn2+ Cu2+ 380 nm (10-5M), 178 pH = 5 NiII Trien+ CuII EDTA Ni2+ 550 or 590 nm 179 -7 (10 M), pH =8, 5% NiII Tetren + CuII EDTA EDTA Stopped flow mixing (10-8 M), 190 pH =7-12, 5-10% NiII Tetren + CuII TTHA Tetren Polarographic (10-5 M) pH 191 =8.0 NiII Trien + CuII EDTA Tetren 550 nm (10-5 M) pH =7.4 181 2+ -8 II Hg 413 nm (10 M) pH=6-7 176 Mn + , , , -TPPS 2+ -7 II Cd 413 nm (10 M) pH=8.0 177 Mn + , , , -TPPS II 2+ -7 Mn +5, 10, 15, 20- Pb 413 nm (10 M) 192 TSPP * Detection limit is given in parenthesis and error in %.

1.8.2 Mechanisms of analytically important catalytic reactions

Indicator reactions for catalytic (non enzymatic) methods may be classified on the basis of reaction mechanisms as follows [193] a. Redox reactions 1. With valency change of the catalyst 2. Without valency change of the catalyst b. Reactions with carbonyl compounds 1. Hydrolysis reactions 2. Decarboxylation reactions c. Exchange reaction with coordination compounds 1. Nucleophilic substitution 2. Electrophilic substitution 3. Coordination chain reactions

Knowledge about the mechanisms of the reactions is far more important for catalytic methods than for methods based on chemical equilibrium. In the latter pocedures, in most cases, proportionality between the concentration of the substance to be determined and on parameter of the reaction at equilibrium is sufficient for analytical purposes, regardless of the stage of reaction at which the equilibrium is attained.

The more knowledge is obtained on the mechanisms of a catalytic reaction, the more easily one will find the most favourable conditions for analytical applications of the reaction with regard to senstivity, accuracy and selectivity.

1.8.2a. Redox reactions

The most common indicator reactions are redox in nature and involve oxidants such as H2O2, O2, BrO3-, ClO3-, IO3-, S2O82-, FeIII, CeIV, etc., and inorganic reductants such as SnII, FeII , AsIII, S2O32- and organic reductants such as amines, phenols, azo dyes and leuco bases of dyes, etc.[194]. Redox reagents can be classified into two main groups, namely, reactants acting by electron transfer through their d-orbitals and reactants acting by electron transfer through their sand p- orbitals (Table 1.7). Reactions with oxidants of the second group are as a rule slower than those of the first group and thus are convenient as indicator reactions for determining catalytically active substances. Table 1.7 Typical Oxidising and Reducing Agents Used for the Determination of Catalysts

d-orbitals

s, p - orbitals ClPolyatomic species dyes,

Oxidising Agents Ce4+ Cu2+ Ag2+ Mn3+ Fe3+ VO2+ MnO4CrO22+ MoO22+ OsO4 Sn4+ Sb5+ Pb4+ Bi5+ Tl3+ H2O2 NO3- ClO3- ClO4BrO3- S2O82- IO4-

Reducing Agents Cr2+ Fe2+ Ti3+ V3+ VO2+ ISn2+ Br-

N3 ArOH, ArNH2, azo leuco bases of dyes AsO2-, S2O32-, C2O42acid

ascorbic

The reactions can be divided into two groups, depending on whether the ion acting as the catalyst changes its oxidation state during the reaction or not.

Reactions in which the oxidation state of the ion-catalyst changes are marked by high sensitivity. Catalyst concentrations from 10-9 to 10-7 g cm-3 may be commonly determined and in some cases (Co, Os, Ru) down to 10-11 g cm-3 . The mechanism of reactions of this type involves the steps Red + C(n+1)+ Cn+ + Ox P +Cn+ (1.47) (1.48)

C(n+1)+ + Z

where and C(n+1)+ and Cn+ are the two diffferent valency forms of the catalyst in the two oxidation states, Red and Ox are the reactants in the redox reaction and P and Z are the reaction products. In these reactions, ions of the transition elements and halides usually function as catalysts.

The other large group of catalytic redox reactions comprises the reactions in which the oxidation state of the ion-catalyst remains unchanged. These include catalytic oxidations by hydrogen peroxide in acidic medium. Catalytic activity is exhibited by cations with high positive charges that readily form peroxocomplexes (e.g. FeIII, TiIV, HfIV, ThIV, NbV, TaV, Cr VI, MoVI and WVI)

General overviews of the mechanism of catalytic reactions of analytical interest have been given by Bontchev [195] and Mottola [20]. 1.8.2b. Reactions with carbonyl compounds and catalytic ligand exchange reactions These catalytic reactions include catalytic decompositions, hydrolysis and catalytic substitution reactions of both organic and inorganic substrates [195].

The reactions are analytically important, because they are often catalyzed by elements from the main groups of the periodic table whose ions have no vacant d-orbitals and thus cannot catalyze redox processes.

The mechanism of catalysis by catalytic decomposition and hydrolysis inolves the effect of the catalyst on the polarization of the bonds in the reactants or on the orientation of the reactants, thus making the reaction possible. An important step in the catalysis is then often chelation : the ions of the catalyst form stable chelates with the substrates. An example is the hydrolysis of monoalkyl phosphates ROPO32-. These substances alone do not hydrolyze in alkaline media. In the presence of Cu2+ or Mg2+ ions, neutral chelates are formed, the negative charge on the substrate is neutralized and hydrolytic decomposition can begin. From the analytical point of view, catalytic substitution reactions of complexes are also important [193].

Typical reactions of this type are the substitution reactions of hexacyanoferrate (II) with various substituting ligands is represented in a simplified form as : [Fe(CN)6]4- + L (1.49) where, L = substituting ligand. Reaction 1.49 is catalyzed by all metal ions that form stable complexes with cyanide (e.g. mercury, silver, palladium, gold) and can be used to determine these metals (198). The Table 1.5 provides a summary of analytical applications of catalysed ligand substitution reactions of [Fe(CN)6]4- and [Fe(CN)6NH3]3- . Other methods based on ligand - exchange reactions are quite recent and have thus been studied less. They have a promising future as they allow the determination of non-transition metals such as alkaline-earth metals as well as of lanthanides ammonia and some other species. Three general types of ligand exchange reaction can be considered in this context, as follows [18, 20]. [Fe(CN)6L]3- + CN-

1.8.2c. Exchange Reaction with Coordination Compounds This category consists of exchange of same ligand between two metal ions, exchange of same metal between two ligands and mutual exchange between metal ions and ligands. 1.8.2c1. Exchange of a ligand between two metal ions The system NiY2- + Zn2+ ZnY2- + Ni2+ (1.50)

Has been described by Margerum et al [196]. This reaction moves slowly and is monitored photometrically at 380 nm by measuring the disappearance of the NiY2- complex. The addition of a small amount of CuII to the system results in two further reactions : NiY2- + Cu2+ CuY2- + Ni2+

(1.51)

CuY2- + Zn2+

ZnY2- + Cu2+

(1.52)

The CuY2- complex is rapidly formed, immediately reacts with zinc ions to form the ZnY2- complex and the CuII ions are liberated. CuII ions are thus not consumed and can be considered as catalyst. Copper ions can be determined on this basis.

1.8.2c2. Exchange of a metal between two ligands Consider the reaction between CuII and the ligands oxybis (ethylenenitrilo) tetra-acetic acid (EGTA) and 4(-2-pyridylazo) resorcinol (PAR) Cu-EGTA + PAR Cu - PAR (1.53)

This reaction is catalyzed by traces of CaII. MgII causes no interference, as its EGTA complex is much less stable than that formed with Ca II. Calcium ions can thus be determined at concentrations between 0.4 and 40 g cm3 by spectrophotometrically monitoring (at 515 nm) the rate of appearance of the Cu-PAR complex [197].

1.8.2c3. Dual exchange reactions (coordination chain reactions) Olsen and Margerum have found, that complex ligand exchange occurs in the reaction of Cu-EDTA with Ni-tren. NiT2+ + CuY2CuT2- + NiY2-

(1.54)

where T = trien = triethylenttramine This reaction develops very slowly, though it can be accelerated by simply adding an excess of one of the ligands. Thus, a small excess of EDTA (Y4) attacks the Ni-trien complex to yield Ni-EDTA and free trien (T), which in turn reacts with the Cu-EDTA complex, from which it displaces the ligand : Y4- + NiT2+ T + Cu Y2NiY2- + T CuT2+ + Y4(1.56) (1.55)

The chain is propagated cyclically and a steady state is rapidly reached. The reaction rate is monitored photometrically by means of the absorbance at 550 nm, which corresponds exclusively to the Cu-trien complex and is proportional to the EDTA (or trien) concentration added. This allows the determination of small concentrations of ligand. Metal ions can act as an inhibitor for the ligand-catalyzed reaction. In this way, trace concentrations (10 -7 to 10-10 g cm-3) of metals forming stable complexes with eg. EDTA canbe determined.

Other examples for the analytical use of substitution reactions are described by Kopanica et al., [31 ,32]. 1.8.3. Application of oscillating reactions This type of reaction has limited but increasing analytical interest. [33]. Reactions catalyzed by metal ions capable of exchanging a single electron at normal potential values between 0.9 and 1.6 V (e.g. the CeIV/CeIII system) are typical representatives of oscillating reactions, as are the Ce IV -catalyzed oxidation of malonic acid (Belousov-Zhabotinski reaction system, B-Z system) succinic acid or citric acid by bromate.

Mechanistically these processes are very complex. For the bromatemalonic acid reaction catalyzed by CeIV-CeIII , a 10-step process for the mechanism has been proposed [33-35]. The process (e.g. B.Z. system) is monitored either by photometric measurement of the changes in the CeIV concentration or by non-equilibrium measurements of the redox potential of the CeIV/CeIII pair, which shows the periodic variation of the CeIV concentration, or by using a bromide-selective electrode.

It is analytically important that the number of cycles per unit of time is proportional to initial reactant concentrations. However, this reactions is only obeyed closely for a short time after the initiation of the reactions; when reagent concentrations, decrease, so does the cycle frequency. The Kinetic determination of hexacyanoferrate (7 10-8 to7 10-6 mol dm-3) by its inhibition of an oscillating chemical reaction (B-Z system) was described by Jiang et. al [36].

1.9. Determination Based on Inhibition The general practice followed for such determination has been to monitor the decrease in reaction rate in a system containing a constant amount of catalyst by adding increasing amount of inhibitor to obtain calibration curves, either by integral or differential rate measurements. This approach offers relatively good limits of detection but has a limit concentration range amenable to determinations. Table I.8 lists some typical redox indicator reaction systems and inhibitors determined by them.

Several other references on the determination of metal ions as well as organic compounds based on their inhibitory action are cited in the literature

[199-205]. Most of these kinetic methods involve redox systems as indicator reactions. From the Table I.8 below it is evident that surprisingly very little attention has been paid to the determination of chemical species based on their inhibitory effect involving ligand substitution processes. Table 1.8 Typical redox systems used for determination of inhibitors by kinetic methods Indicator Reaction 1 Malachite green+Periodate Malachite green+Periodate Catalyst 2 Mn2+ Mn2+ Analyte (Inhibitors) 3 EDTA Glycine, DLPhenylalanine, DL-Glutamic acid, DL-Sarine and LArginine Histamine. Neoantergan and Synopen Nicotinic acid, Nicotinamide, Vitamine B1 and B6 Amino acids in natural water 8Hydroxyquinoline, Bacteriostatics and Fungicides of 8hydroxyquinoline type EDTA and DTPA CYDTA Determination Ref. Range 4 5 10-6 206 10-6M 207

Pyrocatechol violet + Co3+ H2O2 Pyrocatechol violet + Co3+ H2O2 Cu2+ Mn2+

0.1-2.9 109 M 1-5 10-9M

208

209

Luminol + H2O2 Alizarin S + H2O2

0.3-1.1 107 M

210 211

Sb (III)+ Peridoate Phosphinate+ Peridoate Azorubine + H2O2

Mn2+ Mn2+ Mo6+

1-10 10-7M -

212 213

Azorubine + H2O2

Mo6+

Antibiotics 18-160 g/mL 214 (Tetracycline, Methacycline and Demecycline) Gentisic and 6.2-49.3 and 215 chromotropic acid 13.2-105.3

[Fe(Phen)3]3++Cr(IV)

Oxalic acid

Uric acid

g/mL repectively. 0.85216 5.95 g/mL Continued on page. 40

1 Pyrocatechol violet H2O2

Pyridoxal-2 pyridylhydrazone H2O2 4,4'Dihydroxybenzophenone thiosemicarbazone+ H2O2 2,4-Diaminophenol+ H2O2 Autodecomposition of H2O2 p-Phenetidine+Periodate

Table 1.8 (Continued) 2 3 4 5 2+ -6 + Cu Thyroxine and 5- 1-10 10 217 Hydroxytryptophan and 7.732 10-7M 2+ Pb Phosphate and 1 10-7M 218 + Plyphosphates Cu2+ EDTA and EGTA 10-6M 219

Fe2+

Perborate + IPerbromate + IO-Dianisidine+ H2O2 Hydrolysis of sucrose

[Co(III)-EDTA]+ Hypophosphite Sulfanilic acid+Peroxodisulphate Phloxin + Persulphate K4[Fe(CN)6]+pNDA

Oxalate.citrate and fluoride 2+ Cu 1,10phenanthroline 3+ Fe Thiocarbamide, some dithiocarbamtes, pesticides and Mercaptans Zr4+ Fluoride 2+ Fe EGTA, DTPA and EDTA Peroxidase Hg2+ t-Fructofur Hg2+in water and anosidase carbonated soft drink Pd2+ Hg2+in sphalerites and pharmaceuticals + Ag Cysteine Ag+ Hg2+ Cysteine Cysteine, thioglycolic thiosulphate

ng level

220

2-20 g/mL 221 1 102 g/mL 222

1-10 10-9M 1.5-15 107 M 100-270 g/mL 13-120 ng/mL

223 224 225 226

227

228 0.5-4 106 M 1-12 10-6M 229 230

acid,

K4[Fe(CN)6]+Mpz+ K4[Fe(CN)6]+Mpz+

Hg2+ Hg2+

Cysteine MNDT

2.0-20 10- 231 7 M as low as 232 5 10-8M

1.9. Determination Based on Activator In many metal catalysed reactions a substance called activator some times combines with the catalyst to promote the catalytic activity of the metal ion. If the initial rates of such reaction are proportional to the concentration of the activator (until all the catalyst combines with activator), rate measurement can be employed to determine the concentration of activator species the same manner as for direct analysis of catalyst i.e. metal ion (vide supra). Such metal chelate activation may arise due to the fact that a metal chelate can offer labile and free aquo positions on the metal ion through which the reaction with a substrate may take place. In such cases the chelating ligand acts as a carrier for the metal ion and catalysis occurs through the formation of a mixed ligand-chelate compound. Some workers have made use of activators to lower the limits of detection for metal ion catalysts (233). Ascorbic acid, for example, has been used to lower the detection limit of Cu(II) , from 0.05 g/mL to 0.2 g/mL using Cu(II) catalysed oxidation of 2-thiosemicarbazone by hydrogen peroxide [233]. The sensitivity and selectivity of the catalytic determination of vanadium catalyst in the oxidation of o-phenylmediamine by bromate ion is said to be improved by the presence of Tiron acting as an activator [234]. NTA acts as an activator for Mn catalysed periodate - Sb(III) reaction and thus lowers the detection limit of Mn (II) [235].

1.10 Selectivity of catalytic methods of analysis According to IUPAC terminology [236], selectivity denotes the extent to which the method is free of interference by other chemical species. Total or complete specifity is the case in which no interferent effects are known. In practice total specifity is rare for catalytic methods apart from enzyme catalyzed reactions. The catalytic properties of an inorganic ion depends on its size, structure, charge and coordination sphere, chemically similar species exhibit similar catalytic effects and therefore highly selective catalytic determination in the presence of chemically related elements is not common. Consider the indicator reaction

A+ B

(1.57)

which takes place in the presence of catalyst C at a rate defined by the Eqn. 1.57 (1.58)

where A, B are the reactants, k', k are the rate constants for the uncatalyzed and the catalysed reaction, respectively and symbols p', q', p, and q are, in a simple case, the stoichiometric coefficients. In the presence of different catalysts C1,C2,....Cn the expressions for the rate of the catalysed reaction under different reaction conditions can be described by Eqn. 1.59, 1.60. 1- 10 = k11 n- n0 = kn1

11

[C1] + k12 [C1] + kn2

12

[C2] +...........+ k1n [C2] +...........+ knn

1n

[Cn] [Cn]

(1.59) (1.60)

n1

n2

nn

where 1..... n characterise the rates of the catalyzed reaction; i0 the pik qik rates of the uncatalyzed reaction and ik = [A] +[B] , where i, k=1,.....n the coefficients p,q.,,,, are determined by the actual mechanism.

For the activity of a certain catalyst to be highly selective, the activities of the individual catalysts must differ considerably. Under the given reaction conditions, kii kik or, the individual catalysts must react according to different reaction mechanisms i.e. pii, qii pik, qik. The selectivity of a catalytic determination can often be improved by optimizing the procedure by selective masking or by using separation techniques.

The following scheme shows ways to improve the selectivity of catalytic methods. Optimisation of the procedure Variation of reaction conditions pH reagent concentration temperature suitable co-ordination sphere catalyst-substrate interaction

photoactivation mechanism-optimisation (e.g. by means of the graph method)

Use of separation techniques Ion-exchange chromatographic methods - microdiffusin - co-precipitation - distillation - electrophoresis - liquid-liquid-extraction - back-extraction or composition of the organic solvent. - extraction-catalytic determinations

Table 1.9 Survey of the elements which can be determined using the catalytic activity of their ions. The numbers beside the symbols of the elements denote the detection limit expressed as the negative logarithm of the corresponding concentration in g cm-3 [20, 193].

I a

IIa II I Ib V b

V b

VI b

VII b

VI II

ib

II b

II Ia

I V a

V a

VI a

VI Ia

H L i N a K

Be 9 M g6 Ca S 6 c R Sr Y b 7 C Ba L s a F Ra A

B A l6 Z G n9 a C In d6 8

C Si 6 G e7 S n

N P 8 A s5 S b 8 Bi 7

O S1 0 Se 9 Te 10 Po

Ti 8 Zr 8 H r7 T

V 10 N b7

Cr 9 Mo 10

Mn 10 Tc 8 Re 0

Fe 9 Ru 11 Os 11

Co 11 Rh 10 Ir1 1

T W a7 10 Pe U9

N i9 P d 9 Pt 7

Cu 11 Ag 10 Au 9

F1 0 C 17 Br 8 I 10 At

H Ti P g9 b 8

h 7

Liquid-liquid extraction is of greatest importance, followed by ionexchange and other chromatographic methods. In extraction separation the simplest procedure preferable; in other words back-extraction or the thermal decomposition of the organic solvent should be avoided. It is advantageous to carry out the catalytic determination directly in the extract or in the extract dissovled in a mixed solvent (extraction - catalytic determinations) (237).

The following conditions must be satisfied to enable an extraction catalytic determination :

(i)

The indicator reaction must proceed in the organic or mixed solvent and the catalyst activity must be retained in this medium,

An extraction system must be available for a highly selective separation of the test metal and the extraction agent, if extracted itself, must not interfere with the catalytic reaction. Extraction-catalytic methods are very attractive analytically, because they also enable analyses in very complex matrices. Table 1.10 gives an overview of extraction-catalytic methods that have been developed and used until the present time.

(ii)

The nomenclature of kinetic methods of analysis (terms and definitions) is proposed in an IUPAC paper by Svelha [238].

Table 1.10 Extraction-catalytic determination [177] Indicator reaction Extraction System Bromopyrogallol Red (BPR) + S2O82- + 1, 10 Phenanthroline sulphanilic acid + H2O2 + pyridine p-ethoxyaniline +H2O2 1, 10- phenanthroline, BPR/nitrobenzene pyridine, salicylate/CHCl3 neocuproine/CHCl3

Metal Ion Ag

Reaction Medium nitrobenzene-dioxan water -CHCl3-ethanol-water -CHCl3-ethanol-water

Ca

CrVI Fe

3,3'dimethoxybenzidine+H2O2 HCl/MIBK p-ethoxyaniline + H2O2+ 1,10-phenanthroline p-ethoxyaniline + H2O2+ 1,10-phenanthroline p-ethoxyaniline + H2O2+ 1,10-phenanthroline 1-naphthylamine + BrO3o-aminophenol + H2O2 o-phenylenediamine + H2O2 LiCl/MIBK several systems 1, 10 -phenanthroline

MIBK-ethanol-water MIBK-ethanol water CHCl3-ethanol-water CHCl3-ethanol-water

Mo Nb Ti

oxine/ChCl3 CHCl3-ethanol-water benzoin oxime/ CHCl3 CHCl3-ethanol-water pyrocatechol, CHCl3-ethanol-water dioctyl-amine/ butane V o-phenylenediamine + BrO3 pyrocatechol, octylbutanol-ethanol-water dimethylamine/ butanol the kinetics of ligand substitution reactions of transition metal compounds with particular emphasis on their application as analytical tool. Our investigations are aimed at building mechanistic understanding of ligand substitution as well as oxidation reactions that can advance our knowledge of catalytic kinetic methods (CKMs). We determine catalysed and uncatalysed reaction mechanisms by studying chemical kinetics and apply such reactions for the development of inexpensive analytical methods for trace determination of toxicants, environmental pollutants and species of biological interest. The development of methods for determination of toxic species, environmental pollutants and species of biological interest at trace level is challenging analytical expertise especially for complex samples. The specialized instrumentation needed for trace analysis and the associated procedures involved are often very expensive. The Kinetic Methods of Analysis (also called Reaction Rate Methods) utilising spectrophotometric monitoring is an inexpensive analytical method. The CKM continues to be the most popular method in the literature of Kinetic Methods of Analysis. My research group is involved in the developments of CKMs for trace determination of toxicants, environmental pollutants and species of biological interest. It has been demonstrated that it is possible to determine catalytic or inhibitor species (environmental pollutants, toxicants or species of biological interest) by measuring their effects on reaction rates, down to ppm/ppb levels. The cost effective CKMs for the determination of Hg2+, Cu2+, Se2+, Se4+, Ru3+, cysteine, thiosulphate, MNDT (S2C2(CN)22-), NO3-, NO2- etc. in environmental and vegetables samples have been developed using different indicator reactions. The methods are simple, sensitive, selective and economical compared to AAS, radio-istope techniques, mass spectrometry, activation analysis, etc. The undertaken research projects are intended to study regional environmental problems and to develop professional manpower in the area of

development of cost-effective analytical techniques. Hence we have been working on the following research projects: i. Development of catalytic kinetic method for trace determination of mercury(II). Along with understanding the kinetics and mechanism of ligand substitution/oxidation reactions a CKM is being proposed for ascertaining the trace levels of toxic mercury(II). Multi-step Ligand Exchange/Oxidation Reactions A significant contributions towards enhancing understanding the mechanism of ligand exchange reactions can be carried out . A study of the reaction dynamics of relatively slow as well as fast (t = m sec.) reactions and in unraveling the mechanistic features of the reactions occurring in four, five and six steps can be done. The kinetics and mechanism of ligand exchange reactions involving polydentate ligands viz. aminopolycarboxylates, polyamines, polychromics coordinated to Mn(III), Fe(III), Zn(II) and Ni(II) centres by cyanide ions and PAR have been investigated. All these reactions follow variable order dependence in cyanide. The reverse rate is first order in M(CN)x [x = 4, 5, 6; M = metal] and first order in L [L = ligand] and exhibit an inverse first order dependence in [CN-]. These results led us to postulate a multi-step mechanistic scheme in which cyanide ions add one by one to the vacant sites generated by the progressive unwrapping of the ligand coordinated to the metal centres. Besides, the kinetics of catalysed and uncatalysed monodentate ligand exchange reactions of hexacyanoferrate(II) complex with N-methylpyrazinium ion (Mpz+), -nitroso -naphthol, pyrazine, 2-methyl pyrazine (2Mepz), etc. are being investigated followed by their application as analytical tool. Food Chemistry In addition to above areas of research, we have been working on the following projects: i. Exposure to cadmium and arsenic via leafy vegetables in India . This is a collaborative study in which senior chemists of the University of the South Pacific, Dr. Rajendra Prasad. ii. Study of the effects of cooking and deep-freezing on the nitrate concentration in Fijis vegetables using flow injection analysis (FIA). iii. Application of catalytic kinetic method to ascertain the contents of nitrite in water and vegetables samples in Fiji. The flow injection analysis (FIA) and spectrophotometeric techniques have been developed to determine NO3- and NO2-respectively in vegetables and water samples. The methods are being applied to the determination of NO3- in commonly consumed leafy, fruit and root vegetables of Fiji.

Synthesis, Characterization, Antibacterial and Antifungal Studies ofInorganic Complexes To discover the antibacterial and antifungal properties of inorganic complexes, we have been working on the following research projects: i. Synthesis of new molecular receptors based on polypyridyl-ruthenium(II) linked metallo-macrocycles. This is a collaborative study in which senior chemists of the University of the South Pacific, Dr. Rajendra Prasad. ii. An Investigation on Chelating Behavior of Heterocyclic Semicarbazones toward Bioactive Metal ions. iii. An Investigation on Structure and Bonding in Some High Coordinated Complexes of Thorium(IV) and Dioxouranium(VI) Derived from Heterocyclic Semicarbazones as Primary Ligand and Diphenyl Sulfoxide as Secondary Ligand. A series of mono- and binuclear ruthenium complexes of the type [Cp(EPh3)RuL]-/+, [(bipy)2RuL]0/2+, [Ru2Cp2(EPh3)4L], [Ru2Cp2(EPh3)3L] 2+ and [Ru2Cp(EPh3)2(bipy)2]+/3+ [E = P, As, Sb; L = S2C2(CN)22- or (C6H5CH2)S2C2(CN)2] have been synthesized exploiting the nucleophilicity of S and N in L. The complexes have been characterized by microanalysis, conductance, IR, 1H and 31P NMR and UV-visible spectral data. Also synthesis magneto-spectral and thermal characteristics of some lanthanide(III) chloro complexes derived from 4[N-(4-hydroxy-3methoxybenzalidene)amino]antipyrine semicarbazone; 4[N-(3,4,5trimethoxybenzalidene)amino]antipyrinesemicarbazone; 4[(furan-2-ylmethylene)amino]-1,5dimethyl-2-phenylpyrazol-3-one; isonicotinic acid(3,4,5trimethoxybenzylidene)hydrazide and some mixed ligand complexes of thorium(IV) and dioxouranium(VI) with semicarbazones as primary ligand and sulfoxide as secondary ligand and penta-coordinated complexes of oxovanadium(IV) derived from thiosemicarbazones of 4-aminoantipyrine have been carried out. Besides these, synthesis and spectral investigations of some platinum metals ions coordination compounds of 4[N-(furan-2-carboxalidene)amino]antipyrine thiosemicarbazone and 4[N-(3,4,5trimethoxybenzalidene)amino]antipyrine thiosemicarbazone has been carried out. Also, synthesis, magneto-spectral, biological and thermal investigations of cobalt(II) and nickel(II) coordination compounds of thiosemicarbazones derived from 4-aminoantipyrine and hydrazones of isonicotinic acid hydrazide has been done. It has been established that many of the complexes studied have potent antibacterial and antifungal properties/activities. REFERENCES

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