Some organisms used for the biological control of selected weeds
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He has over 25 years of experience in neuro-oncology and minimally invasive surgery techniques. He is a pioneer in many areas in neurosurgery (treatment of brain tumors, Chiari Malformation, and sacroiliac joint disorders).",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"199099",title:"Ph.D.",name:"Vicente",middleName:null,surname:"Vanaclocha",slug:"vicente-vanaclocha",fullName:"Vicente Vanaclocha",profilePictureURL:"https://mts.intechopen.com/storage/users/199099/images/system/199099.jpeg",biography:"Vicente Vanaclocha is Chief of Neurosurgery. Doctor of Medicine from the University of Valencia, he has over 25 years experience in neuro-oncology, minimally invasive and minimally invasive surgery techniques. Specialist in neurosurgery both nationally and internationally (including the General Medical Register of England and stay at the Groote Schuur Hospital in Cape Town, South Africa) has been Chief of Neurosurgery at the University Hospital of Navarra and head of Neurosurgery Service of San Jaime Hospital in Torrevieja. He was also associate professor of neurosurgery at the Faculty of Medicine of the University of Navarra and is a professor of neuroanatomy at the Catholic University of Valencia also serving as an editorial board member of repute.\nCurrently he is Associate Professor at the University of Valencia.",institutionString:"University of Valencia",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"7",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"University of Valencia",institutionURL:null,country:{name:"Spain"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"297737",firstName:"Mateo",lastName:"Pulko",middleName:null,title:"Mr.",imageUrl:"https://mts.intechopen.com/storage/users/297737/images/8492_n.png",email:"mateo.p@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"44996",title:"Integrated Weed Management Practices for Adoption in the Tropics",doi:"10.5772/55950",slug:"integrated-weed-management-practices-for-adoption-in-the-tropics",body:'The earth is undergoing a number of irreversible changes as a result of the activities of man, many of which are adversely affecting the environment. Inappropriate methods of agricultural production, especially those stimulated by efforts in pursuit of short-term gains, have been identified as prime contributors to this environmental degradation.
In earlier times, traditional farming in the tropics involved the use of natural resources in adequate quantity for the sustenance of its population, without diminishing the natural resource base. Key elements of that system included multiple cropping and mixed farming, minimum tillage and water conservation techniques, the use of simple hand tools and other low input technologies.
These sustainable farming methods have been described in pejorative terms as drudgery, laborious, and inefficient. Many have been rejected and new technologies and other high energy based inputs have been embraced. These technologies are costly and heavily foreign-exchange dependent. They also disturb the delicate ecological balance resulting in increased occurrence of pests and diseases, shift in noxious weed populations, soil erosion and pollution of the air and water resources.
The situation in the tropical world is exacerbated as many tropical countries are characterised by conditions that are ideal for the prolific growth and development of a range of plant species. Many of these species are generally non-harmful. However, when inappropriate methods of weed control and/or poor crop management strategies are employed, weeds assume noxious potentials. Ready examples are corn grass (Rottboellia cochinchinensis), white-top (Parthenium hysterophorus) and nutgrass (Cyperus rotundus) [33].
Present farming involves substantial reliance on a range of manufactured inputs. The high dependence on herbicides for weed control in the cultivation of rice, maize, bananas, citrus, sugarcane, onions, white potatoes and vegetable crops is not unnoticed. The competition among suppliers of herbicides has resulted in lower costs of these products which has fuelled their use and abuse in the region.
Low-input, sustainable agriculture addresses multiple objectives from increasing profits to maintaining the environment, and builds on multiple systems as integrated pest management (IPM), integrated weed management (IWM), and crop rotation. Integrated weed management involves the combination of a number of weed control practices that reduces the dependence on any one type of control method and also lowers the input of herbicides. This approach is important for the control of perennial weeds that are inadequately controlled by any single method [8]. The application of IWM also includes the knowledge of past annual and perennial weed populations in fields and weed seed bank [7], competitive crop cultivars, improved crop and soil management practices, and appropriate selection of herbicides [52]. In the context of sustainable agriculture, the concept of IWM seems enlightening and applicable.
The objective of this paper is to discuss the various weed management practices for the control of noxious weeds in major cereal, root and vegetable crops in tropical sustainable agriculture and the strategies used over time to promote their adoption by small farmers.
Integrated weed management systems are based on an agro-ecosystem approach for the management and control of weeds at economic threshold levels [12]. Many farmers in the tropics today practise the same weed control measures as was practised before the introduction of herbicides [35]. The IWM systems approach includes any or a combination of the following practices that give a crop a comparative advantage in competing with weeds.
Prevention strategies include field sanitation and harvesting methods that do not spread weed seeds and vegetative propagules at every step of production (such as seed selection, field preparation, planting, fertilization, irrigation, weed control, harvest and transport) [19]. Such strategies can significantly reduce the infestation of noxious weeds such as nutgrass and white-top [7]. The use of clean crop seed, especially those direct seeded, e.g., maize and legumes, is critical in the prevention of weed problems in new and existing fields. Prevention should be a daily activity, incorporated into the routine of all workers involved in agricultural production, at farm, state and national levels [19]. It is recommended that managers make simple, cost effective modifications to their farm practices to mitigate the risk of introducing new weed seeds to the field. Some of the key considerations as outlined in [19] include:
diligent monitoring for sources of new weed introductions to the agro-ecosystem;
proactive government laws and regulations controlling the introduction and movement of plant materials or soil from one location to another;
destroying vegetative propagules of perennial weeds;
whenever possible, depleting the soil weed seed bank;
propagating seeds and seedling transplants in media free of weed propagules;
preventing weeds from going to seed in crop fields;
cleaning farm machinery before movement into fields;
minimizing the presence of weed seed in livestock feed, manures and composts;
preventing weed seed introduction into rivers and irrigation canals.
For preventive strategies to be fully adopted in an IWM approach, there must be an attitudinal change by farmers and agricultural educators in the tropics. Prevention, although complex, is a very efficient technique for any property size at all crop production stages, from the acquisition of machinery, seed, water and fertilizers, to crop harvest and processing.
Crops differ in their competitiveness with weeds based on their emergence, leaf-area expansion, light interception, canopy architecture, leaf-angle, shape and competitiveness. Within a crop species, cultivars may vary in their competitiveness. While the improved varieties may be high yielding, the traditional varieties exhibit multiple adaptations, competitive ability against weeds and require less agricultural input. The use of competitive crops to discourage weeds is an important IWM strategy. To maximise crop production by minimising the impact of weeds, replacement series and addition series designs have been recommended for intercrop, cover crop and green manure selection [41].
Plant height and leaf area index correlate with competitive ability in row crops. These characters allow the crop to outgrow and cover the weeds. Indeterminate varieties of bean, cowpea, squash and cucumber appear to be better competitive than determinate varieties [38, 39]. The indeterminate varieties of these crops have a vining or spreading habit which allows rapid canopy closure, thus suppressing emerging weeds.
Some plants are able to exude chemical substances which suppress the growth of other neighbouring plants. Research in plants with allelopathic potential is ongoing and has revealed a clearer understanding into the genetics of allelopathic activity in certain crops [29].
Smother crops are quickly established and usurp the resources that weeds would otherwise use. The suppression of weeds may be through both competition (resources) and allelopathy [11]. Smother crops include cowpea (Vigna unguiculata), forage soya beans (Glycine max L.Merril), Sudan grass (Sorghum bicolor subsp. drummondii), kudzu (Pueraria phaseoloides) and pumpkins (Cucurbita maxima), which are very effective in suppressing nutgrass (Cyperus rotundus) and small broadleaved weeds.
Row spacing and seeding rate may influence the ability of the crop to compete with weeds for resources and, therefore, may affect weed management [24, 45]. The rapid closure of the crop canopy can be obtained with a reduction in row spacing [1], an increase in seeding rate [42], and selection of varieties with traits that favour rapid canopy development [13]. It has been reported that rows of 38 cm or less could increase yields and reduce tillage and herbicide requirements because of faster canopy closure [1]. Cereal and vegetable crops can compete with weed growth if they are established at the optimum plant population that allows them to more effectively usurp resources. If crops can reduce incident light by 50 % or more, weeds will seldom become a problem [6, 15]. This approach requires closer intra-and interrow spacings and higher crop densities than normally used.
Cover crops have long been used extensively in the tropics for soil and water conservation, to maintain soil structure and enhance soil fertility, especially on steep or difficult terrain. They are often referred to as living mulches. The use of leguminous cover plants to suppress weeds in plantation crops in the tropical world dates back many decades, but the integration of the legumes into arable cropping systems has not been developed to a level acceptable to farmers. Cover crops also contribute to pest management and help to suppress unwanted weeds. Its use has been mainly in plantation crops. The introduction of inexpensive nitrogen fertilizers and herbicides encouraged many farmers to discontinue this practice. Cover crops can be intercropped or interplanted with a crop of economic significance. They work by excluding light and limiting weed emergence. Examples of cover crops in the tropics include: Mucuna pruriens (L.) DC. (velvet beans), Desmodium heterocarpon var ovalifolium and Arachis pintoi Crap. & Greg. (wild or perennial peanut).
Mulches, on the other hand, may be in the natural form of plant or crop residues or in synthetic form as plastic films or woven synthetic fibres. Other non-living mulches can be either natural materials (plant leaves, stalks, straw, compost and dry soil) or synthetic materials, such as polyethylene, which are used widely in pineapple production. The major disadvantages of plastic films are material costs and difficulty in removal after cropping season. Organic mulches or living mulches are considered cover crops, e.g., mungbean (Vigna radiata (L.) Wilczek cv. Local) and have been shown to be an economical alternative to synthetic mulches [36]. Watermelon and tomato farmers in Dominica, West Indies use Guinea grass (Panicum fasiculatum) as a mulch and cover crop. The grass is killed using a weed killer such as paraquat, and when it re-grows, it is brush-cut before crop emergence or otherwise left as a residue. The crop is planted directly into the cover crop residue which enhances soil and water conservation and protection from wind.
In root crops, for example cassava, live green legumes e.g. Desmodium heterophyllum (Willd) DC [20] with bean (Phaseolus sp.) have been used successfully. Both legumes gave better weed control and crop yields than the herbicide and mulch treatments and Desmodium\n\t\t\t\t\t\theterocarpon var ovalifolium in banana [25]. Stylosanthes guianensis (Aubl.) SW, too, has been used as a cover crop to suppress weeds in cassava [43, 44]. Legume and dry mulch covers are beneficial because they improve soil organic matter and nutrient status, prevent erosion and suppress weeds [30]. The use of legume covers is, however, expensive because of the cost of seeds and labour for their establishment [53, 56]. It is important to use legume and other crop covers which will not compete with the crop for resources. Moreover, any crop cover used must directly benefit the farmer if adoption of the practice is to be sustained.
Some of the weed species that are easily smothered by live legume covers include: Ageratum conyzoides L., Alternenthera sessilis L. R. Br. ex Roth, Mimosa invisa Mart, Digitaria orizontalis Willd, and Panicum maximum Jacq. However, some sedges and grasses like Cyperus rotundus L (purple nutsedge), Rottboellia cochinchinensis (Lour) Clayton (Raoul grass), Sorghum halepense L. Pers (Johnson grass) and Ipomoea sp. (morning glory) are noxious weeds and difficult to control in root and cereal crops [20, 46].
Both cover crops and mulches offer great agro-ecological potential. They serve as a physical barrier against weed emergence, both conserve the soil and improve the ecological balance of the soil, enhance crop yield and provide several environmental services. These new technologies, however, are not easily accepted by small farmers in the tropics. Notwithstanding, they offer a complex combination of interrelated practices which include: (i) necessary practices so as to ensure the production and retention of sufficient mulch and (ii) complementary practices in order to be able to grow a crop and/or maintain yield levels. This typically implies several adaptations to the entire farm production system. Whether mulching actually is a viable component for smallholder conservation farming in developing countries depends on a number of factors, including bio-physical, technological, farm level and institutional factors. The combination of these factors determines the feasibility of and the economic returns to mulching practices—and thereby farmer acceptance.
The development and dissemination of cover crops and mulches for small farmers in tropical developing countries highlights a number of promising experiences, particularly among banana growers i in St. Vincent, in the Caribbean [25]. The technology offers significant savings through reduced tillage and alleviation of some major crop production constraints such as water conservation, timeliness of land preparation and crop establishment.
The basic principles of IWM which include: suppression of weed growth, prevention or suppression of weed seed production, reduction in weed seed bank and prevention or reduction in weed spread, are key elements of all improved husbandry practices. All crop husbandry practices, particularly precision placement and timing of fertiliser application, enhance maximum stimulation of the crop and minimum stimulation of the weed population. Additionally, the use of clean certified seeds, clean farm implements, effective seedbed preparation and seeding methods that improve crop growth, all reduce weed competition [7, 36]. Other management practices including: cultural weed control (intercropping, early planting, optimum plant crop density, and tillage), chemical (minimum herbicide) weed control, mechanical weed control and hoe weeding, have been shown to reduce the competitive effects of weeds on vegetable and cereal crops growth, development and yield [36].
Weeds have a life cycle synchronised to that of the crop such that more weeds emerge with the crop with the onset of rains [33]. Intermittent wetting and drying of weed seeds brought about by early rains preceded by dry spells break seed dormancy [8]. Tillage operations bring buried weed seeds to the surface where they germinate. However, early planting of the crop gives the crop a competitive advantage over the weeds [33, 35].
Judicious irrigation practices such as the use of clean water, channels and canals, can reduce the spread of weed seeds to uninfested fields [3, 38]. Flooding is an important component of weed management in rice in the tropical world. In irrigated and flooded systems, the environment in which weed seeds have to germinate is characterized by the existence of low oxygen concentrations. Differential responses between rice and weeds to flooding could be an important component of weed management for the direct-seeded rice crop, since rice is tolerant to flooding, but many weeds, e.g., Cyperus iria, Fimbristylis miliacea, Leptochloa chinensis, Ludwigia hyssopifolia and similar weed species are not. However, the timing, duration, and depth of flooding and intensity and frequency of irrigation are critical if germination and growth of a number of weed species are to be effectively suppressed.
Irrigated and upland rice and cereal crops are typically grown with few agricultural inputs. A wide range of weeds infest upland rice, many of which are pan-tropical, including the grass weeds: Digitaria spp., Echinochloa colona, Eleusine indica, Paspalum spp., and Rottboellia cochinchinensis, and the broadleaf weeds: Commelina spp., Ageratum conyzoides, Portulaca oleracea, Amaranthus spp. and Euphorbia spp. The variability of weed species composition in upland rice tends to be greater than in the other production systems, and is dependent upon the ecology the cropping system and the management practices used.
Once weed seedlings have emerged and passed the seedling stage, their growth will not be reduced by flooding. In an irrigated environment, there was no emergence of Leptochloa chinensis when rice was flooded 5 days after seeding, but its emergence increased to more than 70 plants m-2 when flooding was delayed until 20 days after seeding. In such situations where water is not readily available, early flooding would make the best use of water to control weeds. Introducing flooding after herbicide application or weeding or hoeing could help reduce future weed growth and the need for additional interventions [17, 27].
Inter-row cultivation is practical in widely spaced row crops, such as maize, vegetables, sugarcane and banana [8, 19], which have interrow distances of 60 cm or more. Interrow cultivations are done by tractor drawn implements or hand operated rotary tillers. The efficiency of this method is higher than manual methods. Minimum tillage, on the other hand, involves the use of the minimum amount of tillage required for crop production for meeting the tillage requirement under existing soil and climatic conditions [56]. It refers to eliminating excess tillage, e.g., reducing four secondary tillage steps to two [8]. Both operations complement and enhance the efficiency of minimum herbicide input through soil incorporation of pre-plant herbicides.
Successive inter-row cultivation has been effective in reducing weed growth and density. Many weed species exhibit morphological plasticity in response to environmental variation and density. Weeds can compensate for density changes so that total biomass per unit area is held relatively constant. Inter-row cultivation improved crop yield by 33% and 78% [20]. However, herbicide application resulted in yield increases of 57 to 300% [27]. Benefits from inter-row cultivation can be limited by in-row weed growth. Most uncontrolled weed growth occurs in the uncultivated area adjacent to and within the crop row. Therefore, the integration of other mechanical or cultural methods often improves with inter-row cultivation. Inter-row cultivation also has potential as a means of controlling late flushes of weeds, but it should not be considered a stand-alone weed management technique since significant in-row weed growth may limit benefits [7].
Tillage operations have a major impact on distribution of weeds in the soil, weed survival and persistency [8, 10], weed species diversity in a given cropping system [15] and the selection pressure on the weed population. Although not much research has gone into the effect that tillage has on tropical weeds, studies have shown that grass weeds, Setaria spp and Corchorus tridens were higher under the ripper and basins compared to conventional tillage. Also, broadleaf weeds were less in minimum tillage compared to conventional tillage. Rotation with conventional tillage systems controls the grasses and perennials but other weeds or weed groups may assume numerical dominance. To balance the pressure of tillage, there may be need to consider rotational tillage where appropriate [35].
Tillage affects vertical weed seed distribution in a soil profile and this seed distribution affects weed seed germination by influencing the soil environment surrounding the seeds [12, 13]. There is less soil disturbance with minimum or zero-till systems and, as such, most of the weed seeds are on or near the soil surface after crop planting. In systems with high soil disturbance using conventional tillage, mixing weed seeds uniformly in the tilled-soil depth has been found to be beneficial. It was also found that on direct-seeded rice, 77% of the weed seeds were retained in the top 2 cm soil layer under a zero-till system, whereas soil disturbance under a conventional tillage system resulted in 62% of the seeds being buried to a depth of 2-5 cm. The seeds were not present in the 5-10 cm soil layer in the zero-till system [22, 23].
The conditions for seed germination are conducive near the soil surface and therefore there is high germination of the weed seeds that are close to the soil surface under zero-till systems, for example, Ageratum conyzoides, Eclipta prostrata, Echinochloa colona, Digitaria ciliaris and Portulaca oleracea. The weed seed populations on the top that are not dormant are easily destroyed by the stale seedbed practice. In this practice, weed seeds are allowed to germinate after a light irrigation or shower and are then killed by using a non-selective herbicide or shallow tillage. This practice helps to reduce the size of the weed seed bank in the soil [8]. Conservation agriculture, or zero tillage farming, is an effective solution to stopping agricultural land degradation, for rehabilitation, and sustainable crop production intensification in the tropics [21, 22].
Herbicide use continues to be one of the most important tools in weed management. However, an IWM approach creates an opportunity to reduce herbicide rates and in some instances, just forgo the use of herbicides altogether.
Given the high cost of herbicides in the tropics, smallholders sometimes either reduce the herbicide rate or mix with other herbicides with differing modes of action. These practices are not without risk. Oftentimes, smallholders realise that these practices are inconsequential and there is no recourse with pesticide retail outlets regarding poor herbicide performance if label rates have not been followed. Yet, farmers often cut rates as a cost saving strategy.
The effectiveness of a reduced rate usually depends on the type of herbicide, weed species present, weed pressure, environmental conditions and, of course, the competitiveness of the crop stand. If the weed pressure is high or the weeds are under stress, it is probably advisable to use an integrated approach. However, reduced rates of herbicide may lead to some level of herbicide resistance and thus the approach to be taken must be carefully considered.
The extent of herbicide use in the tropics is closely related to the cost and availability of labour. Large scale rice and banana production in the tropics receive more than two herbicide applications. However, in the smaller farms, only about 50% of the rice area is treated, particularly where rural labour is available. Herbicides replace hand weeding and enable direct seeding which is less labour demanding, compared to transplanting. Herbicides are also used in the transplanted systems, though to a much lesser extent, and in systems particularly where crop rotation is practised.
There is a need to reduce herbicide input in crop production which can complement cultural practices. With proper timing and selected application methods, good control may be achieved with one-fourth to one-half rates of application [7]. Herbicides are becoming more expensive, and by reducing the pesticide load into the environment, the risk of pollution is reduced. This can be achieved by:
banded application of herbicides
the use of low volumes to improve glyphosate performance
proper timing of post emergence herbicides
the use of herbicide combinations at low rates
the use of newer, more active and more rapidly degradable herbicides, and
monitoring fields to achieve spray decisions
Using lower herbicide dosages would reduce expenditure on herbicides to a fraction of the cost of full label herbicide rates while maintaining efficacy and other benefits derived from herbicide use. Research has revealed that half the recommended dosages of atrazine and nicosulfuron resulted in the lowest weed biomass. Mixing a third of the recommended herbicides of Atrazine and Nicosulfuron resulted in equivalent weed control to the atrazine label recommended dosages. Weed seed production was reduced. Reduced herbicide dosages may fit into the economics of the small farmer and hence has the potential to be a ‘small hammer’ in the IWM programme [51]. However, as mentioned before because of the risk of herbicide resistance, this decision must be taken carefully.
Crop and herbicide rotation reduce selection pressure on weeds and this allows for the development of resistant ecotypes and biotypes [35]. Crop rotation should include crops with either different cultural practices or morphology that will upset the life cycle of weeds as in white-top (Partheniuim hysterophorous) and corn grass (R. cochininensis) [7, 33]. Crop rotations and crop diversification are useful tools for weed management, as they encourage operational diversity that in turn can facilitate improved weed management [31]. Manipulating different planting and harvesting dates among crops provides more opportunities for producers to prevent either plant establishment or seed production by weeds. If sufficient differences exist in the germination requirements of crops and weeds, then seed date can be manipulated to the benefit of the crop for example. Weeds then germinate after canopy closure and they become non competitive [35].
However, in the small farm production systems, crop diversification in rotation and even crop succession are limited. The effectiveness of crop rotation in weed suppression may be enhanced by crop sequences that create varying patterns of resource competition, allelopathy, soil disturbance and mechanical damage to certain species. Diversified crop rotations are likely to provide best opportunities for exploiting diverse sets of tactics and ecological processes to suppress weeds [57]
There are only eight modes of action in available herbicides, and as a consequence rotating herbicides is as important as alternating crops, as overuse will increase the risk of single-, cross-, and multiple resistance [29].There is also the potential for a “species shift,” as new weed species take over when the population of another diminishes, as a result of an effective herbicide or other control practice. Resistance, however, poses a more serious problem, as it depends on the weed species, the efficacy of the herbicide, and the frequency of herbicide use. Continuous use of a particular herbicide will contribute to resistance, and farmers should rotate two or three herbicides [49]. Additionally, using herbicides with the same mode of action will create an environment for resistance development. To reduce the risk of resistance the following guidelines should be considered:
Alternate non-chemical with chemical control methods.
Rotate herbicides, including mode of action of herbicides with the same site of action. Example, Maverick is a sulfonylurea herbicide and Pursuit is an imidazolinone herbicide, but both are group 2 herbicides.
Tank mix different modes of action to apply different types of materials.
Rotate crops which differ in their competitiveness against weeds based on life cycle, growth habit, maturity length, etc., so rotating to different crops can help prevent some weed species from becoming dominant in a given field and control “suspect” herbicide-resistant weeds as if they were an invasive weed species.
Multiple management practices can be used in an integrated plan to prevent or delay the development of herbicide-resistant weed populations. In addition, avoid using herbicides with the same site of action in both fallow years and in the succession crops. Herbicide diversification is the key to preventing resistance, since using one system will create resistant weeds. Herbicide rotation is critical to maintaining grade and delaying resistance. Rotating herbicides with multiple modes of action is critical to delaying the spread of resistance and preventing weeds and volunteers [27].
Currently, there is an increase in the number of resistant weed biotypes, including those resistant to glyphosate, PPO, ALS, dicamba and triazine chemistries. The rapid growth of Respect the RotationTM is a testament to the urgency with which thousands of growers treat the issue of weed resistance [36]. Glyphosate-resistant weeds are spreading at alarming rates from rampant infestations; 358 biotypes have developed resistance to one or more herbicide groups, including glyphosate, PPO, ALS, dicamba and triazine chemistries.
Intercropping or relay cropping systems are based on the principle that space should be occupied by crops and not weeds [57]. Relay cropping can be practised by market gardeners who harvest their crops by hand. These crops should be planted in such a way that the intercrop provides an effective canopy to shade weeds, or that previous crop residue can be used as a mulch to prevent weed growth in successional crops, e.g., pigeon pea (Cajanus cajan) interplanted with maize (Zea mays). Occasionally, the second crop in some intercropping systems is for the purpose of weed management. Crops such as velvetbean (Mucuna pruriens), lablab (Lablab purpureus), Desmodium heterocarpon and tropical kudzu (Pueraria phaseoloides) have been used successfully as intercrops in banana (Musa sp.), cassava (Manihot esculenta) and maize for the management of weeds such as watergrass (Commelina sp.) and cogongrass (Imperata cylindrica) [18, 25, 26] across tropical environments. It was found that intercrops may inhibit weeds by limiting resource capture by weeds or through allelopathic interactions [31], and that weed biomass was reduced in 90 % of the cases when a main crop was intercropped with a “smother” crop. It has also been reported that self-regenerating intercrops reduce establishment costs and can provide weed suppression over years [37].
The use of biological agents such as mycoherbicides, insects and pathogens to control weeds in the tropics is not common. However, the potential for its application to control noxious weeds using monophagous/oligophagous natural enemies must not be overlooked [29]. Table 1.0 shows some of the most successful achievements using this method of control which include: water hyacinth (Eichhornia crassipes (Mart.) Solms) using specific insects, white-top (Parthenium hysterophorus L.) using a fungus, Christmas bush (Chromolaena odorata (L.) King & Robins) using an insect and nutgrass (Cyperus spp.) using a fungus.
Classical biological control is the best among the viable options available for sustainable management of invasive weeds, especially where other technologies such as chemical and mechanical control are unacceptable due to cost and adverse impact on the environment [40].
Some of the techniques described for biological control of weeds in developed countries can be safely and efficiently transferred to developing countries with minimal expense for the initial institutional and human-capacity building. It is essential to know the organism to be used as well as the methods for rearing and release and its host range in order to avoid problems with crops. The Code of Conduct for the Import and Release of Exotic Biological Control Agents (FAO, 1996), gives good guidance on how to proceed in order to introduce new exotic organisms for biological control.
\n\t\t\t\tWeeds\n\t\t\t | \n\t\t\t\n\t\t\t\tBiological control agents\n\t\t\t | \n\t\t
\n\t\t\t\tEichhornia crassipes (Mart.) Solms Water hyacinth | \n\t\t\tWeevils: Neochetina eichhorniae, N. Bruchi\n\t\t\t\t Moth: Sameodes albigutalis\n\t\t\t | \n\t\t
\n\t\t\t\tParthenium hysterophorus L. White-top | \n\t\t\tFungus: Puccinia abrupta var. Partheniicola Zygogramma bicolorata Epiblema strenuana | \n\t\t
\n\t\t\t\tChromolaena odorata (L.) King & Robins. Christmas bush | \n\t\t\tMoth: Parauchaetes pseudoinsulata\n\t\t\t | \n\t\t
\n\t\t\t\tLantana camara L. Black sage, Lantana | \n\t\t\tLacebug: Teleonemia scrupulosa\n\t\t\t | \n\t\t
\n\t\t\t\tCyperus rotundus L. Nutgrass | \n\t\t\tFungus: Puccina canaliculata\n\t\t\t\t Dactylaria higginsii Moth: Bactra spp. | \n\t\t
\n\t\t\t\tAmaranthus spp. | \n\t\t\tFungus: Phomopsis amaranthicola\n\t\t\t | \n\t\t
\n\t\t\t\tRottboellia cochinchinensis (Lour.) Corn grass | \n\t\t\tFungus: Sporisorium ophiuri\n\t\t\t | \n\t\t
The traditional top-down approaches, participatory approaches and discovery based teaching methods have all been used to promote integrated weed management.
The top-down method has been by far the most predominant method and widely used in training on weeds and their control. The focus of these sessions was to train farmers how to apply, mostly synthetic pesticides, and emphasised the need for continuous application. Farmers responded well to these instructional approaches given the severe losses they sustain because of the extent and vigour of weed growth in the tropics and the quick, highly visible effect of synthetic herbicide applications. These class and field sessions have been historically conducted either as stand-alone modules in training courses or as part of the general agronomic practices for field crops. Over the years, extension agents conducted these courses in communities or at centralised farmer training centres. The concept of integrated weed management was not part of the landscape at this time.
In the 1990s, the emergence of farmer participatory approaches to educating farmers gained momentum. Although the focus was on Integrated Pest Management (IPM), weed management was incorporated into learning activities. Farmers, for the first time, were presented with the option of applying a mix of weed management strategies instead of a single chemical option. The aim of farmer participatory approaches is to strengthen farmers’ decision-making skills through an understanding of the agro-ecology of their fields. The approach is widely recognised as an integral part of more sustainable and environmentally friendly crop production practices. The flagship method, Farmer Field Schools (FFS), continues to be used as the preferred approach to integrated management mostly of pests and diseases but increasingly included is the management of noxious weeds.
The Farmer Field School approach involved farmers in activities mostly in the field to understand weed dynamics and to involve farmers in decisions to manage weeds using more sustainable approaches. These activities, done on farmers’ fields, have been conducted across the Caribbean as part of the FFS approach to integrated pest management. Farmers have been exposed to different weed management strategies which stressed integrated approaches. FFS have been conducted in St Lucia, Suriname, Trinidad and Dominica [4].
The FFS model is flexible, and, in recent times, one component has been singled out for increased use because of the enhanced learning it provides. Discovery-based learning is based on the principles of experiential learning; farmers are guided by a trained facilitator who draws out their knowledge and helps them construct meanings based on their rich field experiences. This has been done in several countries of the Caribbean. Discovery-based learning activities have been used in St Vincent in a Farmer Participatory Research (FPR) process to manage weeds in bananas [25, 26]. Farmers were encouraged to plant several cover crops on their farms to evaluate the efficacy of these crops on weed control in bananas. As farmers carried out these activities, they took the weekly measurements and did simple statistical analysis. They were able to discover for themselves the benefits of alternative approaches to the pesticide approach both for their health and that of consumers in foreign countries who purchase their bananas.
Farmers in Trinidad have also conducted community experiments using paper, used cartons, grass much, plastic, precision irrigation all in an attempt to evaluate alternative weed management strategies. Farmers have discovered for themselves the effects of the various treatments and some of these have been adopted by farmers who are tending to move to the low pesticide/ organic farming methods.
A mix of adoption strategies has been used over the years in an effort to get the right approach to IWM. No silver bullet has been found. It is a work in progress. Given the diverse weed flora, farming experiences and farmer circumstances in the tropical world, scientists, educators and farmers will have to dedicate increased energies towards finding an approach that is economical, culturally acceptable and environment friendly.
There is a need to encompass weed management into improved/integrated crop management systems and to develop research and development programmes that will facilitate a more comprehensive understanding of ecology, physiology, biochemistry, competitiveness/allelopathic potential and threshold of weeds.
The key to a successful weed management programme is the effective insertion into crop management programmes of those control techniques that will minimise the impacts of weeds not controlled by the competing crop. The dependence on overly generalized and increasingly expensive chemical input packages, developed elsewhere under a different set of conditions, and aggressively promoted by Researchers, Extension agents and Agro-chemical companies, must be broken.
The IWM systems approach fits into the work habit of many farmers and gives more effective control than when only chemical methods are used. In addition, yield improvements in the order of 40 to 100 % are realized. While IWM systems are considered technologically sound, the social and environmental advantages, as well as the economic costs associated with the practice, need to be ascertained. If farmers are not convinced of the economic viability of the system, then the technology no matter how sound will not be adopted.
Stability 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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