Selected papers referring to open spaces and relevant measures.
\\n\\n
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 insufficiency and high price of land have dramatically increased apartment living and as well as people’s willingness [1, 2] to settle in residential units over recent decades [3]. The gradual conversion of courtyard houses to apartments and residential units has led to changes in the function or removal of spaces embedded in Iranian lives [3], illustrated in Figure 1. The vacuum created by the incompatibility of new housing—a significant part of which includes residential complexes and buildings—has caused unfavorable changes in human life [4, 5]. The land price is a major issue that limits individuals’ choices, forcing them to buy units of a small size. Due to land prices, builders and designers prefer to eliminate open and semi-open spaces to increase and replace indoor spaces [3, 6, 7]. Thus, spaces such as indoor and outdoor communication spaces (e.g., balconies) are rarely seen, and the removal of such important spaces from human life is more prevalent nowadays. This modern norm overlooks the necessity of developing housing that conforms to the lifestyle of its residents. What’s more, the number of houses that can satisfy all the needs of Iranian families is too restricted. Thus, this research aims to investigate the removal or negligence of private open spaces that would ordinarily bring enjoyment to residents. Furthermore, this study seeks to share insights that will improve the quality of people’s life environments and ultimately help them benefit more from their home spaces. The research background indicates a gap on how to design balconies that satisfy the residents of residential buildings. A scientific study into this area could be utilized in future projects to help enhance the quality of such home environments (Figures 1–5).
Gradual transformation of Iranian traditional courtyard houses to new apartments.
Samples of Iranian traditional courtyard houses: (a) Abbasi House, Kashan, (b) Tabatabaei House, Kashan, (c) Pirnia House, Yazd, (d) Navab Vakil House, Yazd, (e) Borujerdis House, Kashan, and (f) Ameri House, Kashan; adopted from [8], analyzed by authors.
The second generation of Iranian houses with yard, adopted from [9], analyzed by authors.
Old apartments designed with terraces or balconies as private open spaces [ref: photos are taken and analyzed by researchers, 2019].
Younger than 5-year-old apartments designed with balconies as private open spaces [ref: photos are taken and analyzed by researchers, 2019].
For example, Einifar and Ghazizadeh [10] showed that designing outdoor spaces is less dealt with by designers; rather, their main focus being the interior space of the building, without paying enough attention to the spaces between the outdoor and indoor space. The authors discuss the necessity and importance of designing the lost and forgotten space of buildings like open space, and recommend that designers of residential complexes pay more attention to such spaces.
Extant studies on private open spaces consider a range of views on residential building spaces including behavioral, environmental, physical, perceptual, semantic, and esthetics. What sets the current research apart from past studies into this subject is its seeking which one of these factors is more influential in this statistical population.
Designers are obliged to see all the approaches in designing open spaces while at the same time pay close attention to the aspects regarded as important by the residents. One article [11] examined the three categories of perceptual-semantic, functional-behavioral and physical-environmental factors in a social-cultural context, with the balcony selected as a private open space between the residential unit and the residential area. The main question of this research was what factors affect the quality of the balcony as an intermediate space and what do people expect from its function in different socio-cultural backgrounds? Based on interview, they examined three residential complexes and presented a model containing six factors. The authors concluded that attention to the secondary functions and the multi-purpose nature of intermediate spaces should be among the primary concerns of planning and designing to enhance the quality of life in apartment housing.
Badeie [12], on the other hand, expressed her research findings from a philosophical point of view: wall space-separators are not necessarily the only effective separation and limitation, but the space instruction of walls is characterized by inferential definition of connectivity. Privacy creates protection, security, and confidentiality in the design of appropriate space frame of artifact environment on one hand and fortifies the dynamic and diverse capabilities of space components for coherence on the other hand. The research focused on enhancing the capabilities of walls in creating links and distance; the capabilities resulting from the concepts of privacy and connection enriched the walls’ functionality area in the construction of space (Figure 6).
Use of walls as space separators, by which links and distances can be made, adopted from [9] and analyzed by authors.
Another research [13] emphasizes the need for intermediate spaces, asserting that joint spaces like balconies play the roles of both interior and exterior spaces and are regarded as the distance between outside and inside space. Also, Mir Shahzadeh [14] examined the role of the linking boundary space, such as balcony and porch, etc., in producing meaning.
Christopher Alexander reported a British study in the Architects Magazine (1957) concerning the balconies of apartments and small houses. He stated that two-thirds of people, for their own reasons, have never used balconies that lack privacy. And in “a pattern language” [15], a model is presented for balconies according to physical characteristics; yet only the quantitative aspect is considered in the book—for example, a minimum depth of 180 cm is considered for such spaces.
Pierre Bourdieu, a well-known French sociologist and anthropologist, also acknowledges that different lifestyles will create a distinction in the living space; the higher the social hierarchy, the higher the esthetic properties of space than its functional responses will be. Therefore, we will have distinct spaces based on necessity-favored need or luxury-favored need, an issue that can be reviewed in the balconies, but not in the present article [16].
Research by Mazandarani [17] investigating housing developments from past to present represents the foundations and status of the intermediate space. The importance of the spaces discussed in the article is underlined by the authors, and general rulings on the points that should be considered by the designers are presented. Unfortunately, there is no comprehensive discussion on balconies as discussed in article [17].
Among other international books in this field is the Book of Life between Buildings, which deals with the concepts of public open spaces, and the initial principles that can be used for intermediate spaces [18]. In the book Esthetics in Architecture [19], regarding the interactive spaces of interior and exterior, the author divides such spaces into three categories: (1) architecture without interaction with outside; (2) architecture with interaction with outside; and (3) modern architecture and border distortions.
In another study, in the chapter on zones and thresholds, the importance of focusing on the scopes that provide a correct definition of outside and inside space for the user of environment is presented. It is argued that humans create limits to understand that we belong within this environment and that we are safe. Furthermore, thresholds and passage spaces are places where the environment manifests itself. Stairs, the edges of roofs, gates, doors, balconies, windows, etc. are all regulators of this manifestation and control the penetrability of these borders. These design factors approve the space separation while at the same time create the possibility of physical and visual passages for people. Hence, the author expresses the necessity and importance of addressing such spaces, and expresses the role of such spaces in three parts: (1) use-oriented role (functional); (2) protective role, or a controlled space, through which the perspective can be seen. This role can be divided into two parts, social and physical; (3) the semantic role, being that the signs of each place, according to the common conventions and social traditions, have a special behavior in each corner and within the desired range. About the balconies, the author says: “Balconies are not practically considered as privacy zone and play the role of seeing and being seen more than the terrace and porches” [20].
Another book on this subject is the work of Rudolf Arnheim, which states: no spatial issue is as much an inherent characteristic of an architect’s work given that they should consider the inside and outside spaces as related concepts. That is, indoor and outdoor areas should be considered as components of one concept [21].
To summarize, Table 1 includes all the related literature.
Author or researcher | Year | Subject or title | Theoretical perspective | Approach |
---|---|---|---|---|
Swapan, et al. [22] | 2019 | Understanding the importance of front yard accessibility for community building: a case study of Subiaco, Western Australia | Front yards as semi-public-private areas can play an important role in the residents’ sense of community | Behavioral |
Reuben, et al. [23] | 2019 | Residential neighborhood greenery and children’s cognitive development | The whole study puts an emphasis on the contribution of surrounding open space greenery of residential buildings on the cognitive development on the children, who were raised in such places. | behavioral, environmental, esthetic |
Azad, et al. [24] | 2018 | Effect of housing layout and open space morphology on residential environments—applying new density indices for evaluation of residential areas case study: Tehran, Iran | Putting an emphasis on the vitality of presence of private or public open spaces and the importance of considering them in the construction laws. | Physical-environmental |
Milanović and Vasilevska [2] | 2018 | Influence of private open spaces on the quality of living in low-rise high density housing | The research focuses on the advantages of private open areas | Behavioral physical |
Einifar and Ghazizadeh [10] | 2010 | Typology of residential complexes of Tehran with open space measure | Importance of paying attention to lost spaces such as open spaces in residential buildings | Physical, behavioral |
Einifar and Ali Niaye Motlagh[11] | 2014 | Explaining the concept of outside-inside in in-between spaces of apartment housing “the case study of balcony in three types of Tehran residential complexes | Considering the secondary functions and multi-purpose nature, the intermediate spaces are among the planning, and design needs to improve the quality of life in apartment housing | Physical-environmental |
Badeie [12] | 2002 | Walls-privacy connection | Philosophical review of connection space | Meaning, behavioral |
Rezakhani [13] | 2013 | An introduction to the concept of joint in architecture based on Heidegger methodology of word etymology | Joint etymology | Meaning |
Mirshahzadeh, et al. [14] | 2013 | The role of boundary space in the creation of meaning | Semiotics approach in boundary-connection space | Esthetic, meaning |
Alexander [15] | 1977 | A pattern language: towns, buildings, construction | Physical examination | Physical |
Bourdieu [16] | 2013 | Distinction: A social critique of the judgment of taste. | Effect of lifestyle on spaces | Behavioral |
Haeri Mazandarani [17] | 2009 | Home, culture and nature | Past developments have changed for the present day and represent the foundations of the space between them | Physical |
Gehl [18] | 2011 | Life between buildings: using public space | Expression of the rules of public open space | Behavioral, physical |
Grütter [19] | 2014 | Grundlagen der Architektur-Wahrnehmung | The division of architectural time periods regarding the relationship between inside and outside space | Physical, perceptional |
Von Mayes [20] | 2013 | Elements of architecture: from form to place | The importance of focusing on the scopes as the elements separating inside and outside | Behavioral, physical |
Rudolf Arnheim [21] | 1977 | The dynamics of architectural form | Relation between inside and outside and attention to this in architecture | Meaning, behavioral |
Bentley [25] | 1985 | Responsive environments: a manual for designers | The strong role of designers in designing flexible ways to keep track of the budget | Behavioral, meaning |
Lawson [26] | 2007 | Language of space | It addresses the issue of realm and perceptual mechanisms in space | Behavioral, meaning |
Selected papers referring to open spaces and relevant measures.
Researchers looked at these spaces from different perspectives. But, as it is clear to every researcher, architecture is not meaningful outside of its context and should be designed and developed on the basis of its main context and social, cultural, and physical conditions.
Therefore, this study tries to help architects to define and explode a specific context in order to have optimal design of open spaces in residential buildings of a neighborhood. By using factors that have been previously investigated and extracted by previous studies, this research uses the case study the Kuye Nasr neighborhood to examine the lifestyle of the residents of the residential buildings. It considers the physical conditions of the buildings, the instructions and rules for improving their design quality, and the desirability of open spaces within residential buildings (balconies). The abovementioned factors will be then evaluated and the results will be available to designers as executable and functional factors.
It should be noted that during the research process, it was found out that the residents of residential buildings in Kuye Nasr were more concerned about the functional aspect of balconies. Hence, this component has been emphasized more than several other factors influencing the usefulness of balconies. The main questions that this research tackles are what factors can satisfy the residents of the Kuye Nasr residential buildings regarding their balconies, and what is the association between the influential factors in the desirability of private open spaces?
To achieve this, the concerns, needs, and opinions of the residents of Kuye Nasr were determined through a field study and interviews, based on which a number of factors were extracted. The validity of such factors was then examined by means of a questionnaire; those factors with a higher statistical weight were presented as features that should be applied by designers of balconies.
The interior of each place is distinguished from the exterior and the surrounding environment by various spatial elements. People have always lived in both outside and inside environments and must be active between these two poles. Consequently, both of these currents cannot be separated, but it is possible that the impact of one of them outweighs the impact of the other. In fact, the kind of governing relationship between the external and internal environment is determined by the spatial relationships between these elements. The structuring and arrangement of these relationships (relations between inside and outside) result from the contradiction between them; that is to say, the separation of a protective shelter from the surrounding area on one hand, and the establishment of the relationship between the two locations on the other hand, are essential for human life. This contradiction is revealed only when the characteristics of the inside and outside location are compared. In spite of these contradictions, there are relations between the inside and outside. According to Christian Norberg Schulz, the relations and conditions governing these two create the art of architecture [19].
Many activities take place around low-rise residential buildings with direct access to the outside. What’s more, there is a flow between the inside and the outside; for instance, in order to know what is going on outside, residents can quickly step out or drink a cup of coffee on the stairs. While multi-story buildings, have less inhibiting them from stepping outside and being among their residential community [18].
Therefore, the role and influence of the intermediaries of the outer and inner space (such as the balcony) are not only undeniable, but also quite significant. Hence, by eliminating or ignoring each of them, the interfacing of the inner and outer spaces is disturbed and the quality of spatial sequencing is declined. Therefore, maintaining the identity of such spaces and optimizing their architectural design is of great importance today.
The border between the closed space and the surrounding open space can be understood as the interface of two worlds. The set of elements—the main function of which is to keep the open space from being enclosed— is called a building and plays a significant mobilizing role in the integration of the interior and exterior space. The best example of such spaces is in traditional Iranian architecture. Semi-open spaces have played an important role in traditional architectural spacing in the past and in the Iranian traditional architecture. The appearance and geometry of these spaces get their models from the features of their own surroundings, and these areas have hosted a range of individual and social activities. This character has been constructed simultaneously in the building in past architecture; modern semi-open spaces do not invite such human interactions and past times as they did in the past and generally lack architectural value. Today, semi-open spaces can be a good way to link human life with nature [1].
In Iranian homes, there is always a space between open and closed spaces. Indoor spaces between closed and open spaces are spaces that provide a variety of facilities for activities of the home and the community; such a presence offers a new connection with nature, light, and climate. Indoor spaces in Iranian homes have varied sizes and functions and are as important as open and closed spaces [27, 28]. Having said that, the presence of indoor spaces in the space organization of contemporary houses has dropped significantly. In some cases, the presence of a porch toward the yard creates a usable connector space between the open and closed space. In the upper floors, the covered terraces and balconies are the covered spaces. These spaces usually are not used completely, and in many cases they are presented as an abandoned floor. Although the balconies and terraces today are located along closed spaces, people prefer not to occupy them due to an undesirable view. Rather, residents typically use balconies as a storage. Nevertheless, these balconies can provide both the perspective and light from the northern and southern fronts for closed areas of contemporary houses [17] (Figure 7).
Areas that are located between the inner and the outer spaces of Iranian houses are highlighted in the images, adopted from [9], analyzed by authors.
Many resources that provide designers with information on how to design spaces also include a series of criteria and components about the design of balconies; for example, Neufert et al. stated that balconies are effective factors in increasing the attractiveness of residential units. Balconies also create a space for some activities, such as outdoor play area for kids that can be easily monitored [29]. Furthermore, balconies can be used to rest, sunbathe, study, eat, etc. In addition to the bio-functional aspects required, a space for the flower box in each part of the balcony is needed [30].
According to the Housing Design Handbook on Balconies Under Regulation and Principles, balconies should cater to the following uses: children’s play space, a space for drying clothes, a space for sitting, gardening and planting, keeping pets, etc. [31].
Time Savers Standards for Building Types presents residents’ opinions on what a balcony is ideally used for: people who have discussed much about the balconies and their positive role have emphasized the pleasure of using and sitting outside. In addition, they emphasize the visual expansion of life space and the opportunity to grow plants and use the balconies to store equipment [32].”
Therefore, the following uses are extracted from the studies on the design of balconies: “children playing, relaxing, sunbathing, studying, eating, keeping flowers and plants, drying clothes, sitting, keeping animals, and warehousing equipment.” However, the factors mentioned are very general and it cannot be said that it is definitely welcomed by the residents in the specified neighborhood in which the research is carried out. Therefore, it is necessary to obtain an estimation of these factors and the factors extracted from the interview section, evaluate them quantitatively in the statistical population, and assess their external validity.
The collection method of influential factors in the design of private open areas was discussed in the previous section (interviewing the residents of Kuye Nasr residential buildings and surveying balcony design studies). All collected factors are categorized into six groups as dependent variables, which can affect the quality of a space like a balcony. The components are classified based on a theoretical framework shown in Figure 8.
Influential components in increasing the desirability of private open spaces.
This is a system based on balance and harmony. Regularity, balance, and fit are perceived and viewed automatically by the viewer and recognized for its beauty [19]. The beauty factors of balcony and the presence of greenery on the balcony belong to this category.
These aspects include the hierarchical ordering and functional domains, access hierarchy, spatial hierarchy, and the hierarchy of various functions forming the communication between inside and outside spaces [33]. The functional structure of space affects the occurrence of behaviors in the environment and is simultaneously affected by the behaviors and anticipation of their occurrence [11]. Hanging clothes, sitting in the open air, cooking or barbecuing, smoking, using tools, entertaining children, enjoying a safe space, and escaping people are in this category.
The environment and behavior are so intertwined that it is difficult to separate them. Therefore, human behavior should be defined in an environmental context. In the past, the environment was considered as an independent variable that affected behavior, shaped it, and created it. Consequently, one of the implications of this traditional approach is that human authority over the environment must be limited and the environment must be coordinated with people in a constant and unchanging form. Recently, however, research has been emphasized to have flexible and variable designs for the environments. In fact, people are now the cause of environmental change and are not limited to environmental influences [34]. Climate factors, tranquility and comfort of the balcony, and balcony orientation fall into this category.
Physical factors include physical and visual order, balance in open and closed environments, walls, and physical bordering structure [35]. Proportional factors and the area of the balcony are included in this category.
The most common approach to human psychology is one that considers several inner processes: perceptual reactions to the environment (how people understand and organize environmental stimuli and react to them), emotional and motivational states associated with environmental stimuli (psychological pressure and negative or positive emotions), and cognitive reactions to the environment (estimates of affluence, complexity, and meanings of the environment). This component considers humans as beings that have internal processors and deals more with mental and psychological processes than with obvious behavioral responses [34]. This factor is related to the human mental perception of the living environment. Visual communication, scale, and proportions, creating the sense place attachment and the sense of separation from space, visibility, and perspective from outside to inside and from inside to outside belong to this category of communication. The perception of sky, earth, buildings, surrounding spaces and, in general, the surroundings and relationship with them actually develop through giving meaning to the environment. This component is completely subjective before becoming an objective one [11]. Factors such as the security of the balcony space and the connection of the balcony to the sky fall into this category.
Therefore, based on the title of this article, “Effective factors on desirability of private open spaces in residential buildings”—independent components in a six-class categorization, in line with the following model in Figure 9— have a linear effect on the desirability of private open spaces as a dependent variable.
Theoretical model of desirability of private open areas including five main aspects including physical, behavioral, environmental, perceptual semantic, and esthetic aspects.
The next section investigates the role of the abovementioned components as influential independent factors in the design of a desirable balcony and introduces the methods and statistical patterns used to explore it, a summary of which is shown in Table 2.
Statistical methods and tests | Application | Type of statistical method |
---|---|---|
Frequency and rate of frequency | Describing demographic variables, describing main questions and variables | Descriptive statistics |
Spearman correlation, chi-square test, one sample chi-square, Friedman rankings | Testing hypotheses | Inferential statistics |
Statistical methods.
Kuye Nasr is the name of one of the northwestern neighborhoods of Tehran located in district 2. The main street of Kuye Nasr (Gisha), stretching approximately 1.5 km, directly connects two main highways to each other. Kuye Nasr has well-organized even and odd streets with English architecture and a complete grid-system urban structure with a total of 41 streets.
The reason for choosing this neighborhood as the case study of the research is the systematic grid texture of the district, which caused the lands in this area to be segmented north-south (regular northern and southern streets). Hence, the research and presentation of this proposal is more targeted and systematic compared to situations where buildings are studied in organic texture or other urban structures. Therefore, by distributing the questionnaire in a homogeneous statistical society, the final result will be generalizable and will have a greater external validity in the statistical population (Figure 10).
Aerial map of the neighborhood, adopted from [9], detailed by authors.
The present research is categorized as applied research using quantitative method [36] and, using the results of the study, seeks to help improve and optimize the behaviors, products, structures, and patterns used by human societies.
The researcher photographed residential buildings in the intended texture to primarily extract the design factors of buildings. Next, using the interview method, the researcher collected the views and opinions of the residents of the residential buildings (the statistical population) regarding balconies; the optimal design factors for such spaces were collected by default. In order to ensure and assess the validity of the default factors, statistical studies (quantitative research method through the questionnaire tool and analysis of these data through SPSS 23) were implemented.
This quantitative research method was adopted, in the form of a questionnaire distributed among people over the age of 20 who were living in the area. After the required data was collected, the principles, methods, and results of statistical analysis were used to study the validity and generalizability of hypotheses in the neighborhood.
The statistical population of the study includes the building residents in the Kuye Nasr neighborhood. The reason for choosing Kuye Nasr as the statistical population is the systematic grid texture of the neighborhood, which has led the lands to be segregated as northern and southern (regular northern and southern streets); therefore, the research and presentation of this proposal are more targeted and systematic compared to situations where buildings are studied in organic textures or other urban structures. Therefore, by distributing the questionnaire in a more homogeneous statistical society, the final result will be more generalizable and will have a greater external validity in the statistical population.
The research sampling method was a simple random sampling method. That is, from 20 alleys with even numbers and 20 alleys with odd numbers, two or three residents were selected randomly. After introducing the researcher and purpose of the study, the questionnaires were distributed. In total, 100 questionnaires were completed and analyzed.
The validity of the questionnaire was tested by a non-statistical method; specifically, through confirmation by a number of experts. Experienced professors and PhD students in the field of architecture reviewed and approved each item on the questionnaire.
Cronbach’s alpha was used for the three-item questions. Cronbach’s alpha coefficient was used to assess the reliability of the questionnaire. The most commonly used method for calculating reliability is the Cronbach alpha, which is called the alpha coefficient. The general rule is that the Cronbach alpha value of a scale should be at least 0.7 [37]. The Cronbach’s alpha coefficient of the questionnaire is indicated in Table 3.
Variables | Cronbach’s alpha |
---|---|
Reliability | 0.78 |
Reliability through internal consistency method (Cronbach’s alpha).
As can be seen, Cronbach’s alpha value of the questionnaire is higher than the criterion 0.7, which confirms the reliability of the questionnaire.
A field study of the current balconies in the apartments or houses available in the site (Figures 11, 12) indicates that a large percentage of balconies on the first floors, which have easier access to the street or alley, are changed due to security concerns. That is, the balconies have lost their original form, creating a special irregularity in the facade (as indicated in the figures below). The residents, for example, have fenced the balconies or have covered the open sides, so that they are safer and cannot be seen when they are on the balcony. Therefore, it can be concluded that it is best to design the balconies of the first floors in such a way that security is considered as a significant point in the design. It should be designed such that it does not require future changes by residents.
(a) Northern apartment. (b) Southern apartment.
(a) Southern apartment. (b) Northern apartment.
During their interviews, building residents were asked to identify their primary concerns regarding the balconies so that the researcher can start designing the questionnaire with an appropriate initial perception.
The following requirements of residents in terms of using balconies are as follow: hanging clothes, planting flowers, cooking, having a spare section for putting kitchen appliances that are better kept in the open air, children’s playing, having a view to beautiful landscapes, ventilation, and connecting balconies with kitchen (Figure 13).
Sample plan of a balcony connected to the kitchen, drawn by authors.
The connection between kitchen and balcony is one of the main suggestions and requests made by Nuye Kasr building residents. During the interview process, the following reasons were extracted:
The connection of the open space (balconies are almost the only open space available to the units) and cooking allows easier access to foodstuff and dining when barbecuing, as well as better ventilation of the kitchen while cooking.
A space for sitting and drinking tea, having food, etc.; such a place is better to be connected to the kitchen.
Access to kitchen appliances that are best protected in the open air.
Proximity and easy access of the kitchen to the balcony to irrigate the plants on the balcony.
A place for hanging clothes in the open air and easy access to the kitchen; nowadays, washing machines are embedded in this space.
All of the abovementioned arguments indicate that balconies are better placed and more efficient when connected to the kitchen. Thus, it can be concluded that in the intended neighborhood, the functional dimension of the balcony is highly regarded.
Analysis of questions related to the main research hypothesis indicates that the presence of spaces, such as balconies, is essential in modern residential housing. A total of 99 out of 100 people who answered to the questionnaire agreed with the necessity of a balcony presence in their residential units. The results in Table 4 also illustrate that the significance level of chi-square is less than the assumed value of 0.1, thereby confirming the hypothesis.
Analysis of the demographic part of the questionnaire shows that tenants and homeowners do not differ in their need for a balcony, indicating the importance of designing balcony for residential houses of both types of economic situations. As shown in Table 5, the significance level of the chi-square independent test is 0.507 and is more than the assumed value of 0.10. This means that there is no significant relationship between the status of the residents of being tenant or owner and the need for a balcony.
The activities performed on balconies nowadays are ranked in Table 6.
Type of relationship | Chi-square value | Degree of freedom | Significance level |
---|---|---|---|
Necessity of balcony | 87.36 | 1 | <0.001 |
Chi-square test: investigating the necessity of balcony presence.
Type of relationship | Chi-square value | Degree of freedom | Significance level |
---|---|---|---|
Between owner or tenant and necessity of balcony | 1.356 | 2 | 0.507 |
Chi-square test: investigating the necessity of balcony from owner or tenant point of view.
Rank | Dimensions | Average score |
---|---|---|
1 | Plants | 5.5 |
2 | Hanging clothes | 5.43 |
3 | Sitting in the open air | 5.27 |
4 | Enjoying view | 5.12 |
5 | Cooking and barbecue | 4.80 |
6 | Smoking | 3.49 |
7 | Storage | 3.25 |
8 | Children’s activities | 3.09 |
Friedman test: ranking of activities carried out on the balcony.
The comparison of the average ratings (Table 6) shows that the highest average rating for flowering and planting activity is at 5.55, which means that this is the most common activity on balconies. The activity of hanging clothes with an average of 5.43 and sitting in the open air with an average rating of 5.27 are the next highest ranking activities. The lowest average rating (3.09) is for children’s activity, which indicates that children playing on the balcony have the lowest activity.
It should be noted that considerations such as balcony dimension and area, the presence of greenery on the balcony, the connection of the balcony with the sky, comfort and tranquility of the balcony area, balcony space security, not being observable on the balcony, functionality of the balcony, and the beauty of balcony are the influential factors in the satisfaction of residents of buildings of their desirable private open area.
This topic of desirability and sustainability of private open areas can be extended further based on the following directions:
Implementing new digital technologies including the Internet of things (IoT) [38] and geographic information system (GIS) [39, 40, 41] for monitoring and evaluating the space quality;
Adoption of open space desirability measures in different types of buildings in dense urban areas [42];
Challenges and opportunities for sustainable development of private open spaces to sustainable development of societies [43, 44];
Investigating the process, factors, barriers, drivers, and decision makers using NVivo for analyzing the desirability of open spaces [45, 46];
Analyzing the trend of private open spaces toward sustainable smart cities [46];
Promoting more integrative strategies between stakeholders to improve the quality of private open spaces [47, 48].
This study tries to find ways to optimize the private open spaces of residential buildings; to this end, the required results were obtained through the analysis of the data and with the help of quantitative methods. The results are presented in the form of logical propositions. Firstly, this study recommends that the designers of the Kuye Nasr residential buildings consider security issues so that first-floor residents can use such spaces without the need for changes or extensions to the building’s facade. Secondly, the functional features of balconies are of great importance to residents, and thus, its desirability factors should be paid close attention. Thirdly, the kitchen is the best and most welcoming space to be connected to the balcony. The kitchen offers the most suitable space connection in the buildings, in line with the functional aspect of the balcony. Fourthly, neighborhood building residents advocate for desirable factors including the presence of greenery on the balcony, the connection of the balcony with the sky, the tranquility and comfort of the balcony space, the security of the balcony, not being observable on the balcony, the functionality of the balcony, and beauty of the balcony. Finally, the present study ends with this question for future researchers: to what extent will the desirability of different parts of Iranian homes, which have been forgotten today or lack suitable quality, help improve the quality of their living spaces.
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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