Metal ion vs. log βMY values.
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More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
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The most profound meaning of the Andes comes not from a physical description, but from the cultural outcome of 10 millenia of knowing, using, and transforming the varied environments of western South America ([1]: 34).
\nTropical mountain environments can be approached in a three-dimensional perspective taking into consideration the horizontal or lateral as well as the vertical dimensions of geographical space: Zimmerer [2] speaks of “vertical environments”. In the case of the tropical Andes, the configuration of the natural environments and of the human landscape is further differentiated by the extent of the Cordilleras on both sides of the Equator from the Caribbean coast (about 11°N) to the tropic of Capricorn (about 23.4°S). Facing the Pacific Ocean with its different ocean currents on its western side and the vast interior, lowland areas of the Orinoco, Rio Negro and Amazon watersheds to the east furthermore result in a marked landscape contrast as one crosses the mountain ranges and highland basins from west to east.
\nAs early as 1807, von Humboldt and Bonpland described the vertical arrangement of ecological zones in their famous illustration of climate and vegetation of the Chimborazo in Ecuador [3]. Troll [4, 5] and Lauer [6, 7, 8] described and compared the altitudinal zonation of climatic factors and vegetation in tropical mountains in general and also specifically in the Andes. They distinguished the principal zones of the tierra caliente, the tierra templada, the tierra helada and the tierra nival or nevada from the base to the top of high tropical Andean mountains. They further differentiated between the humid, semi-humid, semiarid and arid Andes and illustrated these zones by their famous three-dimensional altitudinal and latitudinal models. They also showed that the climatic characteristics of the tropical Andes have a major impact on land use, settlements and agricultural activities. Of great significance are in particular critical temperature thresholds, e.g. for the growth of specific tropical cultigens and of the occurrence of frost. In terms of humidity levels, the humid and semi-humid Andes are characterized by between 12 and 7 humid months (precipitation higher than potential evaporation), the arid and semiarid Andes by 6 to 12 arid months (evaporation higher than precipitation). In a generalized model, the author attempted to portray the altitudinal zonation of ecology, agricultural land use, settlements, and health risks for the humid and the semiarid and arid Andes (Figure 1).
\nAltitudinal zonation of ecology and agricultural land use in the tropical Andes (Stadel 1989).
A pioneering contribution to the concept of altitudinal ecological and human zonation was made by Murra [9, 10]. He states that life of the rural Andean world was shaped by the “verticality” of ecological conditions and that families, villages and ethnic communities have traditionally attempted to control as many micro-ecological zones as possible (Control Vertical or Mitimagkuna), the so-called archipiélagos verticales. Drawing on Murra’s work and based on his own research, Brush [11, 12, 13] distinguished three major types of control and integration of Andean ecological zones and resource areas. The “compact type” is one in which different ecological zones occur in close proximity to each other and are easily accessible to the community. In the case of the “archipelago type”, the ecological zones used by a group of peasants are more distant from each other and are often separated by unused areas, thus requiring more extended travel times. This may require the establishment of a series of permanent or semipermanent “colonies”, away from the home community, in these different ecological zones, as well as a system of exchanges between the home community and the colonies based on reciprocity and redistribution. In the “extended type”, each peasant group exploits a single or a few ecological zones, often specializing in certain products, and exchanges goods with other groups living and exploiting other ecozones ([11]: 292-295). In a summarizing overview, Forman [14] has discussed the “verticality concept” with its implications and applications for the Andes. She comes to the conclusion that the verticality models still provide useful guidelines for rural development in the Andes.
\nIn a rather provocative paper, Allan [15] had rejected the “environmental determinism” of traditional altitudinal zonation models, arguing that they are “no longer suitable for characterizing mountain ecosystems now that human activity is directed to new motorized transportation networks linked to a wider political economy and no longer dependent on altitude” ([15]: Abstract, 185). Instead, he proposed an “accessibility model” of land use in a hypothetical mountain landscape. While mountain geographers would agree that a simplistic and unrestricted environmental determinism has to be rejected, many of them (among them [16]: 197-198), based on their empirical findings, have taken the position that mountain people for a long time have adapted to the geofactors of altitude, relief, distance, climate, vegetation, soil and hazard exposure, while recognizing that new developments, among them accessibility, transportation and intensified lowland-highland interactions, have influenced and modified human activities in mountains. In his rural research in Ecuador, Peru and Bolivia, the author [17, 18, 19, 20] identified a vast array of factors influencing agricultural activities and rural land use:
Altitude and relief configuration, erosion and sedimentation.
Distance, proximity or remoteness to service centres and core areas.
Climate, vegetation and soils.
Natural hazards.
Conservation measures.
Access to and distribution of water: precipitation regimes, water rights and irrigation schemes.
Cultural and spiritual traditions and local perceptions and practices.
Age and nature of settlement process.
Population parameters: age and gender structures and mobility and migration.
Land tenure, land ownership, water rights and land reforms.
Access to acceptance of innovation, modernization and new technologies.
“Conscientization” levels, education and training.
Local, regional, national and global market conditions.
Alternative economic activities and employment opportunities.
Access to capital and investment opportunities.
Transportation and communication and social infrastructures.
Local leadership and community initiatives.
Exogenous impact of business ventures, governmental programmes, non-governmental intervention and influences of “expatriates” (e.g. remittances, investments).
For a long time, agriculture has been the backbone of the rural economy and employment and has been the basis for ancient civilizations in the tropical Andes. Andean agriculture is characterized by a great variety of production systems, land-use forms, types of cultivated plants and domestic animals and forms of pastoralism. Due to the constraints of altitude, slope, climate, soil, forest cover in humid parts and barriers of difficult accessibility, only a limited part of the Andean realm is suitable for agriculture. The agricultural core areas are situated in the larger longitudinal and transverse valleys (e.g. the valleys of the Magdalena and Cauca rivers in Colombia; the Patate-Pastaza rivers in Ecuador; the Marañon, Santa Marta and Mantaro rivers in Peru; the Rio Grande in Bolivia; the Central Valley in Chile; as well as the river oases of the semiarid and arid of the Pacific realm in Peru and northern Chile). Other favored agricultural regions are the highland basins (e.g. in the Sabana of Bogotá), the cuencas or hoyas in Ecuador and the wide Altiplano in southern Peru and Bolivia, especially the shores of Lake Titicaca with their favorable microclimate. In addition, the inner flanks of the Cordilleras in the climatic zones of the tierra templada and tierra fría are intensively used agrarian regions. In contrast to the old settled and agriculturally used Andean realm, newer agrarian colonization zones and rural pioneer spaces have emerged at the eastern Cordilleran flanks and valleys in Colombia, Ecuador, Peru and Bolivia. Nonagriculturally oriented core areas are the urban–rural continuum regions of the major cities and metropolises, as well as the larger mining zones and manufacturing districts. Furthermore, population concentrations have developed along major transportation corridors and around principal ports and airports (Figure 2).
\nChimborazo region, Ecuador (Photo credit: Stadel).
Andean agriculture is characterized by a pronounced altitudinal zonation, a result of thermic, hygric and edaphic differentiation. Following the classical altitudinal ecological “belts” from the warm lowlands to the cold highest parts of the ecumene, the tierra caliente, tierra templada, tierra fría and tierra helada, Borsdorf and Stadel [21] distinguish the following major agrarian zones:
Tropical lowland rain-fed farming (Campo de Lluvia) in the tierra caliente (from sea level to about 1000 m in the humid Andes)
Tropical lowland irrigation farming (Campo de Riego) in the tierra caliente in the semiarid and arid realm
Extratropical agrarian foothill zones (foremost the Chilean longitudinal valley and the foothill regions in northwestern Argentina)
Agrarian areas of the tropical Andes in the altitudinal zones of the tierra templada and tierra fría (about 1000 to 4000 m)
Upper zones of field cultivation and pastoralism in the tierra helada (approximately 4000 to nearly 5000 m)
It is evident that water supply, water rights, water use and the management of the water resources are crucial for agriculture and rural sustainable livelihoods. Permanent, periodic or seasonal water scarcity and the high demand and diverse use of Andean water resources by a variety of decision-makers and often conflicting interest groups make water a critical ecological, cultural, economic, social and political issue and challenge. For instance, the excessive water consumption of the irrigated plantations of export-oriented river oases of coastal Peru threatens the water supplies for small-scale farming and rural communities in the upper watersheds. A voracious consumer of water is the powerful mining sector with its dramatic impact on the natural environment, the ensuing critical shortage and the contamination of water in the surrounding rural areas and the landscape degradation. More recently, the water demands in major tourist destinations (e.g. the Cordillera Blanca region, Cuzco and the Valle Sagrado in Peru) may conflict with the interests of farmers and rural residents in these areas. Conflicts may also arise in the use of water between the upper and lower parts of watersheds, between indígenas and non-native regions, between latifundistas and minifundistas and between urban and rural areas.
\nIn a detailed study of a landscape profile of the Ecuadorian Sierra, Stadel [17, 18] investigated the complex ecological, agricultural and rural mosaic from the upper limit of agricultural activities and settlement at the foot of Chimborazo (about 4200 m) through the high mountain basin (Cuenca) of the city of Ambato and the Patate and Pastaza valleys to the foothills of the Eastern Cordillera (about 900 m). Along this altitudinal profile, the following land-use zones can be identified (Figure 3):
The sparsely settled pasture regions of the cool humid páramo at the upper limit of sporadic settlement and patchy niche field cultivation 3200 to 4200 m). The mostly indigenous population suffers from climatic stress and poor access to the market centres of Ambato and Guaranda; however, the indígenas control a large part of the regional water resources.
The upper zone of intensive arable farming (2800 to 3200 m). A vast array of crops is cultivated, mostly in seasonal or annual rotation. In the lower parts, precipitations tend to be insufficient and unreliable, and irrigation becomes necessary.
The high mountain basin (Cuenca) of Ambato, including the adjoining inner Cordilleran slopes (2500 to 2800 m), a mixed urban–rural space. Rural population clusters are located around the dynamic regional market centre of Ambato and are specializing in productive fruit and vegetable growing and also rely on job opportunities in the city. The climate is semiarid, and agriculture depends on irrigation. In the southeastern part, the small enclave of the Salasaca native community gives the cultural landscape a distinct identity.
The agricultural core region along the Patate valley and a major highway corridor to the Oriente, the gateway to the Amazon lowlands (2000 to 2800 m). In the deeply entrenched valley floor, a highly productive irrigation-based hacienda—and minifundio—agriculture contrasts with a mixture of irrigated and nonirrigated small fields. Here, a mixture of vegetables, cereals and fodder crops is grown in a variety of traditional rotation cycles on steep slopes. Above about 2600 m, the irrigation-based agriculture gives way to a mostly seasonal and rain-fed agriculture. The urban centre of Pelileo, located on the major highway to Ambato and the Oriente, is the principal market centre of the region and a new centre of textile manufacturing, especially a production of jeans for national and international markets.
The temperate humid part of the Pastaza valley (1200 to 2000 m). This section is located in the ecological zone of the tierra templada and benefits from the rains which reach this valley from the Amazon lowlands. In the narrow valley floor and lower slopes, a variety of subtropical and tropical fruits and vegetables are grown. In the higher reaches, a mixture of different cops of a temperature, cooler climate. As one proceeds further downstream, the steep slopes are increasingly covered with a dense humid montane forest. The centre of this section is Baños, a regional service centre, a popular site for Ecuadorians and also foreign visitors, as a pilgrimage site and a recreational destination because of its mild climate and thermal waters.
The lowest part of the landscape profile, located in the tierra templada and higher parts of the tierra caliente (900 to 1200 m). This is a permanently warm and very humid zone, characterized by recent colonization agriculture, and a dispersed linear pioneer settlement stretching along the highway. Here, a wide selection of tropical crops is grown in the valley and on patchy forest clearings on the mountain slopes. At the exit of the Pastaza from the Cordillera, the city of Puyo is the booming regional multifunctional centre.
Study region Chimborazo – Puyo, Ecuador (Stadel 1989).
Zimmerer [22] has pointed out that “overlapping patchworks of farm special units are characteristic of the mountain landscapes of Andean regions of Peru and Bolivia. Patchiness and overlap…are shaped by the broad tolerances of major crops, high variability/low predictability of habitat factors, multifaceted cropping rationales of cultivators including their linkages to extraregional influences, and, to varying extents, the sociospatial coordination of crop choice among farmers”. Zimmerer arrived at this conclusion from detailed field studies within the two communities of Pampa Churigua (farmland range 2800 to 3450 m) in the Department of Cochabamba, Bolivia, and of Mollomarca (farmland range 3100 to 4100 m) in the Cuzco Department of Peru. Although a maize/cereal zone of the lower slopes can be distinguished from an upper potato/tuber zone), a considerable mixing of a variety of crops, a patchiness of land parcels and an elevation-related overlap of crop types can be observed. In another contribution, Zimmerer [23]) states that “integrating the conservation of biodiversity by smallholder farmers with agricultural intensification is increasingly recognized as a leading priority of sustainability and food security amid global environmental and socioeconomic change”. This will contribute to an in situ conservation of agrobiodiversity and enhance the smallholders’ resilience.
\nThe traditional pattern of agricultural land use has been profoundly altered in some areas by the locational influences of accessibility to highway arteries and regional market centres (Figure 4). Where topography, soil quality and irrigation potential exist, a specialized cultivation of vegetables, fruit and flowers serves the urban market, in some cases even international markets (e.g. the plantation of cut flowers for global markets in the Sabana de Bogotá) (Figure 5). Other agricultural cores of a specialized, export-oriented agriculture have developed because of an early valorization of favorable ecological conditions (e.g. the coffee-growing zones of the tierra templada in Colombia), or they have been the result of modernization, new technologies and entrepreneurial initiatives (e.g. the cultivation of special vegetables such as asparagus for world markets in the river oases of coastal Peru). Other important specialized agricultural zones are the wine-growing areas of the Central Valley of Chile and of the Cuyo region of Argentina or the legal or illegal plantation of coca bushes on the humid eastern side of the Andes in Bolivia, Peru and Colombia. New consumer demands may also entail a specialization of agricultural strategies. Examples for this are the new quinoa monocultures in the Lake Titicaca region or expanding alpaca breeding on the Bolivian Altiplano. While this specialization may bring enhanced economic benefits to the region, the potentially negative impact on the ecology, regional water resources, land tenure, traditional land use practices and potentially higher farming risks cannot be ignored [19].
\nAmbato market centre and agricultural hinterland, Ecuador (Borsdorf and Stadel 2015).
Greenhouses of commercial flower cultivation, Sabana of Bogotá, Colombia (Photo credit: Stadel).
Metropolitan centres and other important regional capital centres and economic centres have experienced major population growth rates and areal expansions. This has resulted in a massive planned or uncontrolled urban–rural interface of a wider surrounding region and to the emergence of major peri-urban clusters ([21]: 184-188 and 191-192). While this urbanization may bring to the region new housing, attractive landscape amenity sites for affluent urbanites (so-called parcelas de agrado and ciudades valladas, Figure 6), new employment opportunities or enhanced infrastructures, the negative impacts of this “urban invasion” often prevail ([24]: 239). Land speculation and soaring land prices are threatening the survival of small-scale agriculture and the traditional rural livelihoods by a consumption of often fertile irrigated agricultural land and by diverting the water resources from irrigating the fields to a use for urban households and commercial needs. Driven away by this urbanization process, agricultural smallholders are faced with the options of incorporating themselves into the urban agglomeration, to intensifying land use on their remaining plots or to seeking alternative new agricultural areas. Haller [24] has found that farmers in the Huancayo basin have expanded or intensified field cultivation in the higher suni [25] altitudinal belt (3500 to 4000 m), a marginal and poorly accessible agricultural zone with steep and nonirrigated slopes not suitable for year-round cultivation. Using the example of the regional city of Huancayo and the lower Shullcas Valley, Haller and Córdova-Aguilar [26] have demonstrated that urbanization puts pressure on agrarian land use, endangers the environmental integrity of the region and impacts the Huaytapallana Regional Conservation Area.
\nCiudad Vallada Piedra Roja, Chile (Borsdorf and Stadel 2015).
In the Andes, these agglomerations of a dynamic and multifunctional urban–rural continuum represent the most important areas of population growth, land use conversion and excessive densities of buildings and infrastructural developments. These newly emerging or rapidly expanding clusters are facing the challenge of integrated and effective regional planning and policy actions that attempt to regulate the nature of the growth processes, to recognize the interests of urban and rural stakeholders and to harmonize economic goals with ecosystem services.
\nSince early times, mining has played a major role in the economic development of the Andes. With the discovery of rich deposits of the precious ores of gold and silver, mining has resulted in the establishment of working camps and subsequently in the foundation of smaller and larger settlements. The most famous of them were the silver-mining city of Potosí (Figure 7) in current Bolivia and the mercury-producing city of Huancavelica in the Peruvian Sierra. Both of these booming centres of the early colonial mining industry are located at high altitudes, Potosí at close to 4100 m and Huancavelica at 3600 m. After the initial and generally short-lived gold- and silver-mining boom, other mineral deposits became important: copper, tin, zinc, lead, iron ore, salpetre and most recently lithium.
\nPotosí, Bolivia (Photo credit: Stadel).
Unlike farming and agricultural settlements, the development of mining settlements was not related to favorable environmental factors; many mining sites emerged in locations normally considered unfit for settlements: copper mining in the arid Atacama desert and the mining of gold and a range of non-precious ores at high elevations, some of them above the limit of the ecumene of farming and pastoralism. The most striking example for this is La Rinconada in the southern Peruvian Andes, a gold-mining boom town at 5100 m with an estimated population of some 40,000 people. In addition, many mining clusters developed in areas of poor accessibility and the building of adequate transportation lines represented a major challenge. While the development of these mining areas largely superseded environmental constraints, mining and the associated smelting activities had entailed a corollary of environmental impacts, not only for the mining settlements proper but also for a larger surrounding region, e.g. the excessive consumption of regional water resources, deforestation, severe erosion, mass wasting processes and water and air pollution.
\nWhile mining may offer to the regional population often a much needed alternative employment, encourage the development of infrastructures and services and have stimulated regional economies, the mining sector for a long time has been controlled and dominated by outside national and foreign stakeholders who had little interest in a sustainable regional development. Bury [27] portrayed the negative repercussions of mining on traditional land tenure, water rights, agricultural land use and community institutions. Furthermore, the fate of mining tends to be fluid and uncertain, with many mining areas affected by the typical “boom and bust cycles” resulting from an exhaustion of ores or sharply declining global market prices.
\n“The exceptional diversity of landscapes and cultures in the Andes holds rich opportunities for tourism” ([21]: 249). The ecological variety in the tropical and extratropical realm of the Andes ranges from the humid rainforests (selva) and cloud forests (Ceja de la Montaña) to various types of highland grasslands, to thorn steppes, saltpans (salares) and deserts. On the highest summits in the tropics and on lower elevations in the extratropical realm, snow- and icefields cover the mountains. In addition to this extraordinary ecological diversity, the impressive mountain scenery of rugged peaks (most famous of them are the Torres del Paine in Chilean Patagonia or the spectacular, glacier-covered Cordillera Blanca in Peru) of the numerous active and dormant volcanoes; the deeply entrenched valleys (e.g. the Colca Canyon in Peru); the impressive fjord coast of southern Peru, the impressive rivers in the eastern Cordilleras; the mountain lakes, foremost Lake Titicaca; or the vastness of the Peruvian and Bolivian Altiplano, the landscape appeal of the Andes is further complemented by the rich cultural heritage of the region. Among the famous visitor attractions are the pre-Inca sites (e.g. Chan Chan in the coastal desert of Peru; Chavín de Huantar in the eastern Cordilleras of Peru; Tiahuanaco on the Bolivian Altiplano); the impressive monuments and other relics of the material culture of the Incas centred in Cuzco, Machu Picchu (Figure 8), and other sites of the Valle Sagrado. With the Spanish conquest, the Inca culture was superseded and replaced by the Spanish cultural heritage. Visitors are attracted to the colonial towns with their churches, monasteries, museums, plazas and typical colonial houses, to attractive hacienda buildings (many of them converted to elegant hotels) and to pilgrimage sites. Many of the pre-Spanish and colonial cities have been included in the UNESCO World Cultural Heritage list, a fact which further enhances their appeal for tourists. In a generalized model, Borsdorf and Stadel [21] have portrayed the altitudinal zonation in major types of Andean tourism in the tropical and extratropical realm (Figure 9).
\nMachu Picchu, Peru (Photo credit: Borsdorf and Stadel).
Altitudinal zones and forms of Andean tourism (Borsdorf and Stadel 2015).
In addition to the most common type of a sightseeing tourism attracted to the most famous sites, other forms of visiting and tourism can be observed. Ecotourism has been promoted at all altitudinal levels in many ecologically attractive niches. Of particular interest to visitors are the National Parks, the Biosphere Reserves and other types of protected areas. Still rather spotty are various forms of rural or agrotourism, but this type of tourism may still face the barriers of difficult accessibility, substandard accommodation and other facilities, insufficient investment funds and promotion and sometimes also hesitant rural host families and communities. Successful examples are the comunidades of Vicos and Humacchuco in the Cordillera Blanca region of Peru, to the north of the major mountain tourist centre of Huaraz [28]. With the support of the Instituto de Montañas in Huaraz, the local population was involved in various ways in a gentle, ecologically and culturally compatible and sustainable rural tourism.
\nUnder the motto “cuidar la vida en las montañas” (protecting life in the mountains), some communities around the Huascaran National Park (founded in 1975) benefit from this initiative and are participating in all stages of the planning and management of rural tourism. Ecotourism and “soft” agrotourism are contrasting with newer forms of sports, adventure or event tourism (e.g. mountain biking, paragliding, white-water rafting, modern festivals). Mountaineering, here called andinismo, has a long tradition and appeals to a national and international clientele. Preferred destinations are the high Cordilleras, notably the Cordillera Blanca and Cordillera de Huaylas of Peru, the Cordillera Real in Bolivia and the Patagonian Cordillera of Argentina and Chile.
\nWith progressive urbanization, rural spaces have lost some of their former demographic weight and economic importance. Nevertheless, rural populations continue to represent a large share of the tropical Andean states, and the rural realm forms an important part of national identities and cultures. Economically, many areas can still be rated as marginal spaces, but many regions are important as diversified agrarian areas, as water reservoirs, as mining sites, as destinations for urban amenity migrants and tourists and most important as livelihoods for people. Some rural core areas have become new growth poles and arenas for development and modernization; other regions, in particular the poorly accessible and resource-deficient areas, are threatened by natural hazards, by poverty, stagnation and marginalization, aggravated by political, economic and social neglect and discrimination. External influences and impulses pervade the entire rural realm, even the remote areas. Today, electronic information and communication media bring rural people in touch with national and global developments. In addition, temporary or permanent out-migrants furnish their home community external information, in many cases also remittance cash flows or investments. This has a significant economic, social and cultural impact on their former home communities. Further external actors are government agencies, an array of non-governmental organizations, international institutions and powerful corporations and companies. The consequence of these impacts are significant “livelihood transitions” and “place transformations” [29] which may even transform some Andean core regions into globalized spaces [30].
\nThe result of these multiple endogenous and exogenous influences may have positive or negative impacts on rural communities and livelihoods:
\nIn some of the more accessible areas, technological innovations and market developments have stimulated agricultural developments and changes in crop patterns, leading to serious consequences for exchange relationships and trade between zones. In other zones, people have diversified their livelihood through non-agrarian activities (crafts, wage labour, etc.) or have migrated. ([31]:3).
\nYarnall and Price [32] have examined the impacts of migration and remittance flows on communities in the Valle Alto of the Department of Cochabamba in Bolivia. They observed a “new rurality” transforming the traditional rural environment and society. The communities have benefited by being linked to new “diaspora knowledge networks”, from increased material resources and new stimuli of development. Some formerly poor peasant communities have even become materially better off than nearby colonial towns. But at the same time, the remittance dependence has made these communities vulnerable; as for various reasons, these cash and investment flows may not be reliable and sustainable. Furthermore, traditional forms of agricultural activities and employment may be eroded, and emerging rather sharp economic and social disparities result in a fragmentation of the rural realm.
\nIt follows that rural development is complex, highly differentiated and at times also controversial. A generally accepted approach is to harmonize environmental, sociocultural and economic goals. Bebbington [33] views rural development neither solely rooted in conventional cultural values, economic pursuits and social structures and to the persistence of a subsistence-based economy nor in an uncritical opening to external influences, modernization, new technologies and an unrestricted adherence to national and global market processes. An array of development interventions are directed toward an attenuation of natural risks and their impacts, a protection of natural resources and a preservation of the genetic pool of biodiversity. But these efforts can only have a long-term success if the livelihoods of rural communities and the basic needs of the local population are secured or enhanced in a sustainable fashion [34]. Furthermore, it is today generally recognized that local and regional cultural aspects should be the fundamental basis in the development discourse ([21]: 311). In the past, rural economic development was often guided by external views and strategies without considering the “meaning that campesinos impart to the economy as actors in a social context” ([35], Abstract, 310). Rist therefore pleads for an “actor-oriented approach that is not based on preconceived, nonlocal concepts” (ibid.). This has been referred to as “ethno-development” [36], “development with identity” [37], “participatory cultural development” and other terms. Andolina et al. [38] call this approach “alternative modernities” enabling and mobilizing local human resources and strengthening local ownership and responsibility [39]. Local cultures and the traditional heritage are no longer seen as obstacles and barriers to development, but as enriching, locally accepted and sustainable factors. Local knowledge and practices should not be seen as static and paralyzing, but as dynamic and evolving: “transformed by autochthonous innovations, by an adaptation to changing circumstances, and by an adoption of knowledge, capabilities and technologies” ([40]: 14, translated).
\nBased on his empirical research in the tropical Andes, Stadel [20] derived the following postulates for a “campesino-oriented development”:
Appreciation of the knowledge and experience of campesinos (saber campesino) and strengthening of their cultural pride.
Esteem for the traditions, cultural values, customs and rituals of local communities (lo andino, [41]; sagesse des Andes, [42]).
Strengthening of communal solidarity and cooperation.
Respect for nature (cosmovisión andina) and an aspiration to harmonize environment and society.
Exploration of the potentials and limitations of the natural and human environments.
Strengthening of the resilience and adaptive capacities of the local population, facing environmental risks, economic and social vulnerabilities and potential disaster.
Improvement of the living conditions of the population, with a special focus on poor people and enhancement of the infrastructures and services in water supply, sanitation, health, nutrition and housing.
Promotion of environmentally compatible and sustainable forms of agriculture (agroecología) and silviculture and of agricultural niche products.
Enhancement and diversification of alternative income and employment opportunities (e.g. in eco- or agrotourism).
Mobilization of local human resources and creation of attractive local perspectives for young people to stem their migration to cities.
Improved access to microloans and other forms of financial and technical support.
Sensible use of external funds, especially of the remittances, to meaningful types of investment.
Safeguards against economic, social and political discrimination and exclusion and struggles against external exploitation.
Development emphasis on locally perceived and formulated needs, priorities and implementation methods.
Participation, enablement and empowerment in rural development and ownership of projects by local communities.
Enhanced communication channels, accessibility and transport facilities.
Improvement of the quantity and quality of formal and informal education and training.
In a simplified summarizing table (Figure 10), Stadel [20] has proposed a conceptual model for “sustainable campesino communities”. It is argued that campesino communities can benefit by various positive intrinsic factors, as well as by favorable extrinsic factors.
\nSustainable campesino communities – a conceptual model (Stadel 2008).
In spite of rapidly expanding metropolitan centres and a progressing urbanization, the identity of the Andean realm is still rooted in agricultural traditions and in rural societies. Based on the mountainous character but also because of the opportunities for rural living, the Andes can be portrayed as a rich and varied mosaic of agricultural fields, pastures, farms, villages and towns, forming archipelagos of favorable environmental conditions, of human activities, and of cultural heritages. The diversity of rural spaces is the result of the extraordinary variety of natural and cultural traits, both in the horizontal and vertical dimensions of the Andes. In the horizontal perspective, agricultural land use in the tropical regions is distinguished from that of the extratropical one and is also differentiated by climatic influences from the Pacific Ocean or from the continental basins of the Amazon and Orinoco watersheds. Distinct agricultural patterns and rural landscapes are further resulting from the human factors of accessibility to roads and markets, cultural traditions, as well as external impacts.
\nWhile the core and most widespread functional identity of the Andes lies in farming, pastoralism and agricultural settlements, the rural space is also shaped by other activities, foremost mining, industry and commercial activities. More recently, urban real-estate interests have “invaded” selected regions outside larger cities, especially in areas with a specific landscape or climatic appeal. Urban “amenity migrants” have moved into secluded peri-urban clusters, often into “gated communities” (ciudades valladas). Another newer form of rural functional orientation is the recreational appeal and the national and international tourism potential in attractive landscapes and cultural sites. Therefore, the extraordinary complexity of micro-spatial rural clusters has generated an intricate pattern of diverse “archipelagos” in the Andes.
\nThe rural Andes are a dynamic realm undergoing many changes and deep transformations. This applies to agriculture with its adaptation to changing environmental conditions, to new market orientations and in some cases to altered perceptions and strategies of farmers. Rural regions, even in formerly remote locations, are no longer isolated areas; in some cases, they may also no longer be regarded as peripheral spaces. New transportation arteries and communication channels connect rural residents to national core areas, even to global regions and actors. But the changes in the rural realm have not eliminated its disparities, and the “new rurality” has old and new winners and losers. Some regions are stagnating, and some rural people remain poor or are becoming marginalized, while others are dynamic, with its stakeholders progressing and seizing new opportunities.
\nThe viability of the rural Andes is endangered by a number of internal and external threats. The vagaries of the climate and environmental deterioration processes are threatening agriculturally based livelihoods, especially those of small farmers. The persistent imbalance in the land tenure system, rural unemployment and underemployment, poverty and deficient infrastructures and services, combined with the lure of cities and other countries, have depleted many rural regions of the human capital of young and enterprising people. Furthermore, the growing external control of the land and its natural resources by external interests and stakeholders threaten the livelihoods of the rural population.
\nWhat are the options for a sustainable future of the rural Andes? Generally speaking, the rural realm must be effectively assisted to overcome inequality, discrimination, poverty and marginality and thus become an attractive living space and an alternative to the life in large cities or overseas. Rural population should be empowered to control and mobilize their resources and to develop mechanisms for enhanced local autonomy and self-determination. The author has proposed a generalized conceptual model for “sustainable campesino communities”. But every region and community has its own identity, needs and priorities and will undoubtedly find their ways to enable them to seek appropriate development paths, likely in a careful balance between proven environmentally and culturally adapted strategies and new ones, innovative but also sensitive to the environment, societies and cultures of the region: “The pursuit of sustainability is a local undertaking not only because each community is ecologically and culturally unique but also its citizens have specific place-based needs and requirements” ([37]: 1).
\nStability constant of the formation of metal complexes is used to measure interaction strength of reagents. From this process, metal ion and ligand interaction formed the two types of metal complexes; one is supramolecular complexes known as host-guest complexes [1] and the other is anion-containing complexes. In the solution it provides and calculates the required information about the concentration of metal complexes.
Solubility, light, absorption conductance, partitioning behavior, conductance, and chemical reactivity are the complex characteristics which are different from their components. It is determined by various numerical and graphical methods which calculate the equilibrium constants. This is based on or related to a quantity, and this is called the complex formation function.
During the displacement process at the time of metal complex formation, some ions disappear and form a bonding between metal ions and ligands. It may be considered due to displacement of a proton from a ligand species or ions or molecules causing a drop in the pH values of the solution [2]. Irving and Rossotti developed a technique for the calculation of stability constant, and it is called potentiometric technique.
To determine the stability constant, Bjerrum has used a very simple method, and that is metal salt solubility method. For the studies of a larger different variety of polycarboxylic acid-, oxime-, phenol-containing metal complexes, Martel and Calvin used the potentiometric technique for calculating the stability constant. Those ligands [3, 4] which are uncharged are also examined, and their stability constant calculations are determined by the limitations inherent in the ligand solubility method. The limitations of the metal salt solubility method and the result of solubility methods are compared with this. M-L, MLM, and (M3) L are some types of examples of metal-ligand bonding. One thing is common, and that is these entire types metal complexes all have one ligand.
The solubility method can only usefully be applied to studies of such complexes, and it is best applied for ML; in such types of system, only ML is formed. Jacqueline Gonzalez and his co-worker propose to explore the coordination chemistry of calcium complexes. Jacqueline and et al. followed this technique for evaluate the as partial model of the manganese-calcium cluster and spectrophotometric studies of metal complexes, i.e., they were carried calcium(II)-1,4-butanediamine in acetonitrile and calcium(II)-1,2-ethylendiamine, calcium(II)-1,3-propanediamine by them.
Spectrophotometric programming of HypSpec and received data allows the determination of the formation of solubility constants. The logarithmic values, log β110 = 5.25 for calcium(II)-1,3-propanediamine, log β110 = 4.072 for calcium(II)-1,4-butanediamine, and log β110 = 4.69 for calcium(II)-1,2-ethylendiamine, are obtained for the formation constants [5]. The structure of Cimetidine and histamine H2-receptor is a chelating agent. Syed Ahmad Tirmizi has examined Ni(II) cimetidine complex spectrophotometrically and found an absorption peak maximum of 622 nm with respect to different temperatures.
Syed Ahmad Tirmizi have been used to taken 1:2 ratio of metal and cimetidine compound for the formation of metal complex and this satisfied by molar ratio data. The data, 1.40–2.4 × 108, was calculated using the continuous variation method and stability constant at room temperature, and by using the mole ratio method, this value at 40°C was 1.24–2.4 × 108. In the formation of lead(II) metal complexes with 1-(aminomethyl) cyclohexene, Thanavelan et al. found the formation of their binary and ternary complexes. Glycine,
Using the stability constant method, these ternary complexes were found out, and using the parameters such as Δ log K and log X, these ternary complex data were compared with binary complex. The potentiometric technique at room temperature (25°C) was used in the investigation of some binary complex formations by Abdelatty Mohamed Radalla. These binary complexes are formed with 3D transition metal ions like Cu2+, Ni2+, Co2+, and Zn2+ and gallic acid’s importance as a ligand and 0.10 mol dm−3 of NaNO3. Such types of aliphatic dicarboxylic acids are very important biologically. Many acid-base characters and the nature of using metal complexes have been investigated and discussed time to time by researchers [7].
The above acids (gallic and aliphatic dicarboxylic acid) were taken to determine the acidity constants. For the purpose of determining the stability constant, binary and ternary complexes were carried in the aqueous medium using the experimental conditions as stated above. The potentiometric pH-metric titration curves are inferred for the binary complexes and ternary complexes at different ratios, and formation of ternary metal complex formation was in a stepwise manner that provided an easy way to calculate stability constants for the formation of metal complexes.
The values of Δ log K, percentage of relative stabilization (% R. S.), and log X were evaluated and discussed. Now it provides the outline about the various complex species for the formation of different solvents, and using the concentration distribution, these complexes were evaluated and discussed. The conductivity measurements have ascertained for the mode of ternary chelating complexes.
A study by Kathrina and Pekar suggests that pH plays an important role in the formation of metal complexes. When epigallocatechin gallate and gallic acid combine with copper(II) to form metal complexes, the pH changes its speculation. We have been able to determine its pH in frozen and fluid state with the help of multifrequency EPR spectroscopy [8]. With the help of this spectroscopy, it is able to detect that each polyphenol exhibits the formation of three different mononuclear species. If the pH ranges 4–8 for di- or polymeric complex of Cu(II), then it conjectures such metal complexes. It is only at alkaline pH values.
The line width in fluid solutions by molecular motion exhibits an incomplete average of the parameters of anisotropy spin Hamilton. If the complexes are different, then their rotational correlation times for this also vary. The analysis of the LyCEP anisotropy of the fluid solution spectra is performed using the parameters determined by the simulation of the rigid boundary spectra. Its result suggests that pH increases its value by affecting its molecular mass. It is a polyphenol ligand complex with copper, showing the coordination of an increasing number of its molecules or increasing participation of polyphenol dimers used as ligands in the copper coordination region.
The study by Vishenkova and his co-worker [8] provides the investigation of electrochemical properties of triphenylmethane dyes using a voltammetric method with constant-current potential sweep. Malachite green (MG) and basic fuchsin (BF) have been chosen as representatives of the triphenylmethane dyes [9]. The electrochemical behavior of MG and BF on the surface of a mercury film electrode depending on pH, the nature of background electrolyte, and scan rate of potential sweep has been investigated.
Using a voltammetric method with a constant-current potential sweep examines the electrical properties of triphenylmethane dye. In order to find out the solution of MG and BF, certain registration conditions have been prescribed for it, which have proved to be quite useful. The reduction peak for the currents of MG and BF has demonstrated that it increases linearly with respect to their concentration as 9.0 × 10−5–7.0 × 10−3 mol/dm3 for MG and 6.0 × 10−5–8.0 × 10−3 mol/dm3 for BF and correlation coefficients of these values are 0.9987 for MG and 0.9961 for BF [10].
5.0 × 10−5 and 2.0 × 10−5 mol/dm3 are the values used as the detection limit of MG and BF, respectively. Stability constants are a very useful technique whose size is huge. Due to its usefulness, it has acquired an umbrella right in the fields of chemistry, biology, and medicine. No science subject is untouched by this. Stability constants of metal complexes are widely used in the various areas like pharmaceuticals as well as biological processes, separation techniques, analytical processes, etc. In the presented chapter, we have tried to explain this in detail by focusing our attention on the applications and solutions of stability of metal complexes in solution.
Stability or formation or binding constant is the type of equilibrium constant used for the formation of metal complexes in the solution. Acutely, stability constant is applicable to measure the strength of interactions between the ligands and metal ions that are involved in complex formation in the solution [11]. A generally these 1-4 equations are expressed as the following ways:
Thus
K1, K2, K3, … Kn are the equilibrium constants and these are also called stepwise stability constants. The formation of the metal-ligand-n complex may also be expressed as equilibrium constants by the following steps:
The parameters K and β are related together, and these are expressed in the following example:
Now the numerator and denominator are multiplied together with the use of [metal-ligand] [metal-ligand2], and after the rearranging we get the following equation:
Now we expressed it as the following:
From the above relation, it is clear that the overall stability constant βn is equal to the product of the successive (i.e., stepwise) stability constants, K1, K2, K3,…Kn. This in other words means that the value of stability constants for a given complex is actually made up of a number of stepwise stability constants. The term stability is used without qualification to mean that the complex exists under a suitable condition and that it is possible to store the complex for an appreciable amount of time. The term stability is commonly used because coordination compounds are stable in one reagent but dissociate or dissolve in the presence of another regent. It is also possible that the term stability can be referred as an action of heat or light or compound. The stability of complex [13] is expressed qualitatively in terms of thermodynamic stability and kinetic stability.
In a chemical reaction, chemical equilibrium is a state in which the concentration of reactants and products does not change over time. Often this condition occurs when the speed of forward reaction becomes the same as the speed of reverse reaction. It is worth noting that the velocities of the forward and backward reaction are not zero at this stage but are equal.
If hydrogen and iodine are kept together in molecular proportions in a closed process vessel at high temperature (500°C), the following action begins:
In this activity, hydrogen iodide is formed by combining hydrogen and iodine, and the amount of hydrogen iodide increases with time. In contrast to this action, if the pure hydrogen iodide gas is heated to 500°C in the reaction, the compound is dissolved by reverse action, which causes hydrogen iodide to dissolve into hydrogen and iodine, and the ratio of these products increases over time. This is expressed in the following reaction:
For the formation of metal chelates, the thermodynamic technique provides a very significant information. Thermodynamics is a very useful technique in distinguishing between enthalpic effects and entropic effects. The bond strengths are totally effected by enthalpic effect, and this does not make any difference in the whole solution in order/disorder. Based on thermodynamics the chelate effect below can be best explained. The change of standard Gibbs free energy for equilibrium constant is response:
Where:
R = gas constant
T = absolute temperature
At 25°C,
ΔG = (− 5.708 kJ mol−1) · log β.
The enthalpy term creates free energy, i.e.,
For metal complexes, thermodynamic stability and kinetic stability are two interpretations of the stability constant in the solution. If reaction moves from reactants to products, it refers to a change in its energy as shown in the above equation. But for the reactivity, kinetic stability is responsible for this system, and this refers to ligand species [14].
Stable and unstable are thermodynamic terms, while labile and inert are kinetic terms. As a rule of thumb, those complexes which react completely within about 1 minute at 25°C are considered labile, and those complexes which take longer time than this to react are considered inert. [Ni(CN)4]2− is thermodynamically stable but kinetically inert because it rapidly exchanges ligands.
The metal complexes [Co(NH3)6]3+ and such types of other complexes are kinetically inert, but these are thermodynamically unstable. We may expect the complex to decompose in the presence of acid immediately because the complex is thermodynamically unstable. The rate is of the order of 1025 for the decomposition in acidic solution. Hence, it is thermodynamically unstable. However, nothing happens to the complex when it is kept in acidic solution for several days. While considering the stability of a complex, always the condition must be specified. Under what condition, the complex which is stable or unstable must be specified such as acidic and also basic condition, temperature, reactant, etc.
A complex may be stable with respect to a particular condition but with respect to another. In brief, a stable complex need not be inert and similarly, and an unstable complex need not be labile. It is the measure of extent of formation or transformation of complex under a given set of conditions at equilibrium [15].
Thermodynamic stability has an important role in determining the bond strength between metal ligands. Some complexes are stable, but as soon as they are introduced into aqueous solution, it is seen that these complexes have an effect on stability and fall apart. For an example, we take the [Co (SCN)4]2+ complex. The ion bond of this complex is very weak and breaks down quickly to form other compounds. But when [Fe(CN)6]3− is dissolved in water, it does not test Fe3+ by any sensitive reagent, which shows that this complex is more stable in aqueous solution. So it is indicated that thermodynamic stability deals with metal-ligand bond energy, stability constant, and other thermodynamic parameters.
This example also suggests that thermodynamic stability refers to the stability and instability of complexes. The measurement of the extent to which one type of species is converted to another species can be determined by thermodynamic stability until equilibrium is achieved. For example, tetracyanonickelate is a thermodynamically stable and kinetic labile complex. But the example of hexa-amine cobalt(III) cation is just the opposite:
Thermodynamics is used to express the difference between stability and inertia. For the stable complex, large positive free energies have been obtained from ΔG0 reaction. The ΔH0, standard enthalpy change for this reaction, is related to the equilibrium constant, βn, by the well thermodynamic equation:
For similar complexes of various ions of the same charge of a particular transition series and particular ligand, ΔS0 values would not differ substantially, and hence a change in ΔH0 value would be related to change in βn values. So the order of values of ΔH0 is also the order of the βn value.
Kinetic stability is referred to the rate of reaction between the metal ions and ligand proceeds at equilibrium or used for the formation of metal complexes. To take a decision for kinetic stability of any complexes, time is a factor which plays an important role for this. It deals between the rate of reaction and what is the mechanism of this metal complex reaction.
As we discuss above in thermodynamic stability, kinetic stability is referred for the complexes at which complex is inert or labile. The term “inert” was used by Tube for the thermally stable complex and for reactive complexes the term ‘labile’ used [16]. The naturally occurring chlorophyll is the example of polydentate ligand. This complex is extremely inert due to exchange of Mg2+ ion in the aqueous media.
The nature of central atom of metal complexes, dimension, its degree of oxidation, electronic structure of these complexes, and so many other properties of complexes are affected by the stability constant. Some of the following factors described are as follows.
In the coordination chemistry, metal complexes are formed by the interaction between metal ions and ligands. For these type of compounds, metal ions are the coordination center, and the ligand or complexing agents are oriented surrounding it. These metal ions mostly are the transition elements. For the determination of stability constant, some important characteristics of these metal complexes may be as given below.
Ligands are oriented around the central metal ions in the metal complexes. The sizes of these metal ions determine the number of ligand species that will be attached or ordinated (dative covalent) in the bond formation. If the sizes of these metal ions are increased, the stability of coordination compound defiantly decreased. Zn(II) metal ions are the central atoms in their complexes, and due to their lower size (0.74A°) as compared to Cd(II) size (0.97A°), metal ions are formed more stable.
Hence, Al3+ ion has the greatest nuclear charge, but its size is the smallest, and the ion N3− has the smallest nuclear charge, and its size is the largest [17]. Inert atoms like neon do not participate in the formation of the covalent or ionic compound, and these atoms are not included in isoelectronic series; hence, it is not easy to measure the radius of this type of atoms.
The properties of stability depend on the size of the metal ion used in the complexes and the total charge thereon. If the size of these metal ions is small and the total charge is high, then their complexes will be more stable. That is, their ratio will depend on the charge/radius. This can be demonstrated through the following reaction:
An ionic charge is the electric charge of an ion which is formed by the gain (negative charge) or loss (positive charge) of one or more electrons from an atom or group of atoms. If we talk about the stability of the coordination compounds, we find that the total charge of their central metal ions affects their stability, so when we change their charge, their stability in a range of constant can be determined by propagating of error [18]. If the charge of the central metal ion is high and the size is small, the stability of the compound is high:
In general, the most stable coordination bonds can cause smaller and highly charged rations to form more stable coordination compounds.
When an electron pair attracts a central ion toward itself, a strong stability complex is formed, and this is due to electron donation from ligand → metal ion. This donation process is increasing the bond stability of metal complexes exerted the polarizing effect on certain metal ions. Li+, Na+, Mg2+, Ca2+, Al3+, etc. are such type of metal cation which is not able to attract so strongly from a highly electronegative containing stable complexes, and these atoms are O, N, F, Au, Hg, Ag, Pd, Pt, and Pb. Such type of ligands that contains P, S, As, Br and I atom are formed stable complex because these accepts electron from M → π-bonding. Hg2+, Pb2+, Cd2+, and Bi3+ metal ions are also electronegative ions which form insoluble salts of metal sulfide which are insoluble in aqueous medium.
Volatile ligands may be lost at higher temperature. This is exemplified by the loss of water by hydrates and ammonia:
The transformation of certain coordination compounds from one to another is shown as follows:
A ligand is an ion or small molecule that binds to a metal atom (in chemistry) or to a biomolecule (in biochemistry) to form a complex, such as the iron-cyanide coordination complex Prussian blue or the iron-containing blood-protein hemoglobin. The ligands are arranged in spectrochemical series which are based on the order of their field strength. It is not possible to form the entire series by studying complexes with a single metal ion; the series has been developed by overlapping different sequences obtained from spectroscopic studies [19]. The order of common ligands according to their increasing ligand field strength is
The above spectrochemical series help us to for determination of strength of ligands. The left last ligand is as weaker ligand. These weaker ligand cannot forcible binding the 3d electron and resultant outer octahedral complexes formed. It is as-
Increasing the oxidation number the value of Δ increased.
Δ increases from top to bottom.
However, when we consider the metal ion, the following two useful trends are observed:
Δ increases with increasing oxidation number.
Δ increases down a group. For the determination of stability constant, the nature of the ligand plays an important role.
The following factors described the nature of ligands.
The size and charge are two factors that affect the production of metal complexes. The less charges and small sizes of ligands are more favorable for less stable bond formation with metal and ligand. But if this condition just opposite the product of metal and ligand will be a more stable compound. So, less nuclear charge and more size= less stable complex whereas if more nuclear charge and small in size= less stable complex. We take fluoride as an example because due to their smaller size than other halide and their highest electro negativity than the other halides formed more stable complexes. So, fluoride ion complexes are more stable than the other halides:
As compared to S2− ion, O22− ions formed more stable complexes.
It is suggested by Calvin and Wilson that the metal complexes will be more stable if the basic character or strength of ligands is higher. It means that the donating power of ligands to central metal ions is high [20].
It means that the donating power of ligands to central metal ions is high. In the case of complex formation of aliphatic diamines and aromatic diamines, the stable complex is formed by aliphatic diamines, while an unstable coordination complex is formed with aromatic diamines. So, from the above discussion, we find that the stability will be grater if the e-donation power is greater.
Thus it is clear that greater basic power of electron-donating species will form always a stable complex. NH3, CN−, and F− behaved as ligands and formed stable complexes; on the other hand, these are more basic in nature.
We know that if the concentration of coordination group is higher, these coordination compounds will exist in the water as solution. It is noted that greater coordinating tendency show the water molecules than the coordinating group which is originally present. SCN− (thiocynate) ions are present in higher concentration; with the Co2+ metal ion, it formed a blue-colored complex which is stable in state, but on dilution of water medium, a pink color is generated in place of blue, or blue color complex is destroyed by [Co(H2O)6]2+, and now if we added further SCN−, the pink color will not appear:
Now it is clear that H2O and SCN− are in competition for the formation of Co(II) metal-containing complex compound. In the case of tetra-amine cupric sulfate metal complex, ammonia acts as a donor atom or ligand. If the concentration of NH3 is lower in the reaction, copper hydroxide is formed but at higher concentration formed tetra-amine cupric sulfate as in the following reaction:
For a metal ion, chelating ligand is enhanced and affinity it and this is known as chelate effect and compared it with non-chelating and monodentate ligand or the multidentate ligand is acts as chelating agent. Ethylenediamine is a simple chelating agent (Figure 1).
Structure of ethylenediamine.
Due to the bidentate nature of ethylenediamine, it forms two bonds with metal ion or central atom. Water forms a complex with Ni(II) metal ion, but due to its monodentate nature, it is not a chelating ligand (Figures 2 and 3).
Structure of chelating configuration of ethylenediamine ligand.
Structure of chelate with three ethylenediamine ligands.
The dentate cheater of ligand provides bonding strength to the metal ion or central atom, and as the number of dentate increased, the tightness also increased. This phenomenon is known as chelating effect, whereas the formation of metal complexes with these chelating ligands is called chelation:
or
Some factors are of much importance for chelation as follows.
The sizes of the chelating ring are increased as well as the stability of metal complex decreased. According to Schwarzenbach, connecting bridges form the chelating rings. The elongated ring predominates when long bridges connect to the ligand to form a long ring. It is usually observed that an increased a chelate ring size leads to a decrease in complex stability.
He interpreted this statement. The entropy of complex will be change if the size of chelating ring is increased, i.e., second donor atom is allowed by the chelating ring. As the size of chelating ring increased, the stability should be increased with entropy effect. Four-membered ring compounds are unstable, whereas five-membered are more stable. So the chelating ring increased its size and the stability of the formed metal complexes.
The number of chelating rings also decides the stability of complexes. Non-chelating metal compounds are less stable than chelating compounds. These numbers increase the thermodynamic volume, and this is also known as an entropy term. In recent years ligands capable of occupying as many as six coordination positions on a single metal ion have been described. The studies on the formation constants of coordination compounds with these ligands have been reported. The numbers of ligand or chelating agents are affecting the stability of metal complexes so as these numbers go up and down, the stability will also vary with it.
For the Ni(II) complexes with ethylenediamine as chelating agent, its log K1 value is 7.9 and if chelating agents are trine and penten, then the log K1 values are 7.9 and 19.3, respectively. If the metal ion change Zn is used in place of Ni (II), then the values of log K1 for ethylenediamine, trine, and penten are 6.0, 12.1, and 16.2, respectively. The log βMY values of metal ions are given in Table 1.
Metal ion | log βMY (25°C, I = 0.1 M) |
---|---|
Ca2+ | 11.2 |
Cu2+ | 19.8 |
Fe3+ | 24.9 |
Metal ion vs. log βMY values.
Ni(NH3)62+ is an octahedral metal complex, and at 25 °C its log β6 value is 8.3, but Ni(ethylenediamine)32+ complex is also octahedral in geometry, with 18.4 as the value of log β6. The calculated stability value of Ni(ethylenediamine)32+ 1010 times is more stable because three rings are formed as chelating rings by ethylenediamine as compared to no such ring is formed. Ethylenediaminetetraacetate (EDTA) is a hexadentate ligand that usually formed stable metal complexes due to its chelating power.
A special effect in molecules is when the atoms occupy space. This is called steric effect. Energy is needed to bring these atoms closer to each other. These electrons run away from near atoms. There can be many ways of generating it. We know the repulsion between valence electrons as the steric effect which increases the energy of the current system [21]. Favorable or unfavorable any response is created.
For example, if the static effect is greater than that of a product in a metal complex formation process, then the static increase would favor this reaction. But if the case is opposite, the skepticism will be toward retardation.
This effect will mainly depend on the conformational states, and the minimum steric interaction theory can also be considered. The effect of secondary steric is seen on receptor binding produced by an alternative such as:
Reduced access to a critical group.
Stick barrier.
Electronic resonance substitution bond by repulsion.
Population of a conformer changes due to active shielding effect.
The macrocyclic effect is exactly like the image of the chelate effect. It means the principle of both is the same. But the macrocyclic effect suggests cyclic deformation of the ligand. Macrocyclic ligands are more tainted than chelating agents. Rather, their compounds are more stable due to their cyclically constrained constriction. It requires some entropy in the body to react with the metal ion. For example, for a tetradentate cyclic ligand, we can use heme-B which forms a metal complex using Fe+2 ions in biological systems (Figure 4).
Structure of hemoglobin is the biological complex compound which contains Fe(II) metal ion.
The n-dentate chelating agents play an important role for the formation of more stable metal complexes as compared to n-unidentate ligands. But the n-dentate macrocyclic ligand gives more stable environment in the metal complexes as compared to open-chain ligands. This change is very favorable for entropy (ΔS) and enthalpy (ΔH) change.
There are so many parameters to determination of formation constants or stability constant in solution for all types of chelating agents. These numerous parameters or techniques are refractive index, conductance, temperature, distribution coefficients, refractive index, nuclear magnetic resonance volume changes, and optical activity.
Solubility products are helpful and used for the insoluble salt that metal ions formed and complexes which are also formed by metal ions and are more soluble. The formation constant is observed in presence of donor atoms by measuring increased solubility.
To determine the solubility constant, it involves the distribution of the ligands or any complex species; metal ions are present in two immiscible solvents like water and carbon tetrachloride, benzene, etc.
In this method metal ions or ligands are present in solution and on exchanger. A solid polymers containing with positive and negative ions are ion exchange resins. These are insoluble in nature. This technique is helpful to determine the metal ions in resin phase, liquid phase, or even in radioactive metal. This method is also helpful to determine the polarizing effect of metal ions on the stability of ligands like Cu(II) and Zn(II) with amino acid complex formation.
At the equilibrium free metal and ions are present in the solution, and using the different electrometric techniques as described determines its stability constant.
This method is based upon the titration method or follows its principle. A stranded acid-base solution used as titrate and which is titrated, it may be strong base or strong acid follows as potentiometrically. The concentration of solution using 103− M does not decomposed during the reaction process, and this method is useful for protonated and nonprotonated ligands.
This is the graphic method used to determine the stability constant in producing metal complex formation by plotting a polarograph between the absences of substances and the presence of substances. During the complex formation, the presence of metal ions produced a shift in the half-wave potential in the solution.
If a complex is relatively slow to form and also decomposes at measurable rate, it is possible, in favorable situations, to determine the equilibrium constant.
This involves the study of the equilibrium constant of slow complex formation reactions. The use of tracer technique is extremely useful for determining the concentrations of dissociation products of the coordination compound.
This method is based on the study of the effect of an equilibrium concentration of some ions on the function at a definite organ of a living organism. The equilibrium concentration of the ion studied may be determined by the action of this organ in systems with complex formation.
The solution of 25 ml is adopted by preparing at the 1.0 × 10−5 M ligand or 1.0 × 10−5 M concentration and 1.0 × 10−5 M for the metal ion:
The solutions containing the metal ions were considered both at a pH sufficiently high to give almost complete complexation and at a pH value selected in order to obtain an equilibrium system of ligand and complexes.
In order to avoid modification of the spectral behavior of the ligand due to pH variations, it has been verified that the range of pH considered in all cases does not affect absorbance values. Use the collected pH values adopted for the determinations as well as selected wavelengths. The ionic strengths calculated from the composition of solutions allowed activity coefficient corrections. Absorbance values were determined at wavelengths in the range 430–700 nm, every 2 nm.
For a successive metal complex formation, use this method. If ligand is protonate and the produced complex has maximum number of donate atoms of ligands, a selective light is absorbed by this complex, while for determination of stability constant, it is just known about the composition of formed species.
Bjerrum (1941) used the method stepwise addition of the ligands to coordination sphere for the formation of complex. So, complex metal–ligand-n forms as the following steps [22]. The equilibrium constants, K1, K2, K3, … Kn are called stepwise stability constants. The formation of the complex metal-ligandn may also be expressed by the following steps and equilibrium constants.
Where:
M = central metal cation
L = monodentate ligand
N = maximum coordination number for the metal ion M for the ligand
If a complex ion is slow to reach equilibrium, it is often possible to apply the method of isotopic dilution to determine the equilibrium concentration of one or more of the species. Most often radioactive isotopes are used.
This method was extensively used by Werner and others to study metal complexes. In the case of a series of complexes of Co(III) and Pt(IV), Werner assigned the correct formulae on the basis of their molar conductance values measured in freshly prepared dilute solutions. In some cases, the conductance of the solution increased with time due to a chemical change, e.g.,
It is concluded that the information presented is very important to determine the stability constant of the ligand metal complexes. Some methods like spectrophotometric method, Bjerrum’s method, distribution method, ion exchange method, electrometric techniques, and potentiometric method have a huge contribution in quantitative analysis by easily finding the stability constants of metal complexes in aqueous solutions.
All the authors thank the Library of University of Delhi for reference books, journals, etc. which helped us a lot in reviewing the chapter.
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