\r\n\tThe sense of proprioception includes various aspects or submodalities such as position sense, motion sense (kinaesthesia; including the duration, direction, amplitude, speed, acceleration and timing of movements), force tension sense, and change in velocity sense.
\r\n
\r\n\tProprioception is mediated by proprioceptors, a specialized subset of about 10-15% of mechanosensory neurons localized in dorsal root ganglia that convey information about the stretch and tension of muscles, tendons, joints and perhaps the skin. So, the neurological basis of proprioception originates from proprioceptors with contact specialized sensory organs in muscles (muscle spindles), tendons (Golgi tendon organs), joints (different morphotypes of sensory corpuscles including Ruffini’s corpuscles and Pacinian corpuscles) and the skin (cutaneous mechanoreceptors). Thereafter, the information originated in the proprioceptors forming complex nerve pathways reach the central nervous system at the level of the spinal cord, the cerebellum and the cerebral cortex for processing. Hence, proprioception can be regarded as a continuous loop of feedforward and feedback inputs between sensory receptors throughout the body and the nervous system.
\r\n
\r\n\tIn limb and axial muscles, the proprioception originates in the muscle spindles. Nevertheless, the cephalic muscles, with the exception of the extraocular muscles and those innervated by the mandibular branch of the trigeminal nerve, lack muscle spindles. But the facial or pharyngeal proprioception plays key roles in the regulation and coordination of facial musculature and diverse reflexes. At the basis of these functional characteristics are the multiple communications between cranial nerves. Substituting muscle spindles by other kinds of proprioceptors might be at the basis. \r\n\tOn the other hand, since the stimuli for proprioceptors are mechanical (stretch, tension, and so) proprioception can be regarded as a modality of mechanosensitivity. During the last decade progress has been made to understanding the molecular basis of mechanosensitivity. However, identity of mechanotransducers is poorly know. The mechanogated ion channels acid-sensing ion channel 2 (ASIC2), transient receptor potential vanilloid 4 (TRPV4) and PIEZO2 have been related to mechanotransduction and have been detected in proprioceptors innervating muscle spindles and Golgi tendon organs in mice. Also, mice lacking Piezo2 showed severely uncoordinated body movements and abnormal limb positions. \r\n\tFinally, the lesion of the proprioception receptors, proprioceptors or the nerve center and pathways related to proprioception result in poor proprioception. Importantly, age-related changes also affect proprioception due to a combination of natural age-related changes to the central nervous system, nerves, joints, and muscles. Acute and long-term impairment can be related to toxicological, medical or injury conditions, but also with neuromuscular and central nervous system diseases.
\r\n
\r\n\tBased on the above comments this book intends to provide a comprehensive update an overview of the anatomical, structural and molecular basis of proprioception as well as of the main causes of proprioception impairment and possible treatments.
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1. The environmental impact in urban green space maintenance
1.1 The fast expansion of maintenance workload in urban green space
The increase of the urban green space leads to the expansion of maintenance workload. During the years 2000–2018, due to the 2.6 times growth of the urban built-up area in China (from 2,152,500 ha to 5,622,500 ha), the urban green space increased from 778,200 ha to 2,921,300 ha (Figure 1). The dramatical extension of the urban green space increased the maintenance pressure directly. This point can be reflected by the fast increase of the maintenance equipment used in urban green space. Figure 2 shows that the number of maintenance machine increased 5 times between the year 2000 and 2018, from 44,238 to 228,019 in the Chinese city [1].
Figure 1.
The increase of urban built-up and green space area in China (2000–2018).
Figure 2.
The increase of maintenance equipment used in Chinese urban green space (2000–2018).
The functional expansion of urban green spaces has also increased the workload of maintenance. In the past 40 years, the development goal of urban green space in most parts of the world has changed from “quantity” to “quality” [2]. Take China as an example.
The extensive growth period of the urban green space was from 1990 to 2004. With the intention of the “garden city” proposed by the Ministry of Construction, most cities began to expand the green area and pursue high greening rates [3]. During this period, many urban reservations were filled with woodland and lacked maintenance.
From 2005 to 2014, urban green space growth began to focus on the richness of vertical plant layers. This dramatically increases the maintenance workload. With the goals of the “National Forest City” and “Ecological Garden City” proposed by the State Forestry Administration and the Ministry of Construction, the development of urban green space has turned to forest vegetation as the main body, enriching the vertical plant level to improve ecological functions [4]. Multilevel plant communities require more maintenance tasks to maintain the shape or function of each plant layer than traditional woodland green spaces [5]. During this time, the growing maintenance workload has forced city managers to consider increasing productivity and reducing resource consumption to save on maintenance budgets.
In the year 2015, the General Office of the State Council issued the “Guiding Opinions on Promoting the Construction of Sponge City” [6]. This framework aimed to exert the natural ecological functions of the urban green space, to increase the urban eco-securities, such as absorption, infiltration, and sustained release to the rainwater, and decrease the maintenance requirement in simultaneously [7]. That can deliver a clear message that the city managers have to seek a more natural plant combination method to release the maintenance pressure in the future plant community design and management in urban green space.
1.2 The maintenance tasks in urban green space
The maintenance tasks in urban green space include trimming, irrigation, fertilization, and pesticide [8]. During the maintenance record in the urban green space in Zhengdong New District (2018, Zhengzhou, China), the annual trimming frequency in woodland, hedge, and grassland was 1–3 times, 6–10 times, and 13–22 times separately; the average irrigation frequency was 30–50 times/year; the fertilization frequency was 2–4 times/year; the centralized pesticide frequency was 2–5 times/year. In addition, it also includes the removal of plant waste after every time of the trimming work.
The maintenance of green space is related to strong labor work and machine input. According to the official regulation of the number of maintenance team in Zhengdong New District, in a total of more than 460 ha urban green area, they totally configured about 900 site conservation workers responsible for daily maintenance (0.3 ha/per person at 70 ha of CBD area, 0.6 ha/person at other green areas). Besides, the trimming/mowing work is related to the application of power chainsaw, hedge/edge strimmer, and lawn mower. Sprinklers are required for irrigation and pesticide work. Trucks are required for the removal of plant waste and transportation of the maintenance materials.
1.3 The energy consumption and emission discharge in green space maintenance
The maintenance work in urban green space includes the consumption of energy resources and the discharge of waste to the environment, with annual cycles [9]. In daily maintenance, most trimming work and plant waste transportation depend on machine use. This machine work mainly consumes fossil energy and emits harmful gases (including CO2, NOx, CH4, etc.) into the atmosphere. Irrigation mainly consumes urban tap water. The fertilizer and pesticide consumed in fertilization and pest control work can produce soil carbon residues. Besides, the trucks responsible for fertilizer transportation and drug spraying also need to consume fossil energy and generate exhaust gas [10, 11].
The fossil energy (gasoline, diesel, etc.) consumed in green space maintenance is named direct energy (DE) consumption, which can be converted with standard coal that releases the same amount of heat during combustion. The use of water resource, fertilizer, and pesticide is named indirect energy (IDE) consumption. The IDE consumption also has the equivalent conversion coefficient with the calorific value of standard coal, and ultimately all show the consumption of heat energy [12, 13]. Among the harmful gases emitted by green space maintenance, greenhouse gases (GHG) have been recognized as the main source of atmospheric pollution, which account for more than 83% of the total emissions [14]. This energy consumption and exhaust emissions persist with the annual cycle of maintenance tasks.
Although the purpose of maintenance is to provide a safe and healthy development for the green space, which is able to continue the service for the urban public, this long-term human intervention in the green space itself also violates the basic requirements for the sustainable development: maximization of self-renewal and minimization of the artificial disturbance [15]. Therefore, reducing the environmental impact caused by maintenance tasks will contribute to the sustainable development of urban green space.
1.4 The literature review of environmental impact in urban green space maintenance
Few urban environment assessment systems are mentioned about the environmental impacts of green space maintenance. The University of Florida, in the “Florida-Friendly Landscaping Guidelines,” proposed that the maintenance team should sign a contract with the green space owners and enact a detailed working plan before maintenance operations. The working plan should estimate the types of maintenance tasks and detail workload. This is important to improve working efficiency, save maintenance materials, and reduce environmental impacts [16]. The “Sustainable Sites Initiative” (proposed by the US Lady Bird Johnson Wildflower Center and US Botanic Garden) point out that during the complete life cycle of the urban landscape (design, construction, operation, maintenance, and disposal), the maintenance procedure occupied around 10–20% of the total environmental impact [17].
Some research point out reducing the maintenance workload can decrease the environmental impact and improve the ecological benefits of the green space. Zhao and Liu pointed out that the city managers should reduce the area of grassland and plant more native woodland to improve the adaptability and tolerance of urban green space. Extensive use of wildflowers and meadows can also benefit to the urban wildlife and reduce the maintenance requirement [18]. Guo in the renewable and recyclable landscape research indicated that the self-maintenance green space is able to maximize the utilization of energy and materials and reduce environmental pollution in the use process [19]. Min put forward that the conservation green space is to improve the utilization rate of maintenance resources and energy use and obtain the maximum ecological, environmental, and social benefits [20]. Shu-Hua pointed out that symbiotic cyclic urban landscape architecture should adopt the design of low environmental impact, including the selection of recyclable, low-consumption, and high-durable building materials, and pay attention to reduce the maintenance material input in the later period [21].
The quantitative study on the environmental impact of urban green space maintenance is limited. After finishing 3 years of urban green space maintenance carbon emission data collection for the three major cities, Seoul, Chuncheon, and Gangneung, Hyun found that the annual increase of urban green space carbon emissions is between 10 and 20%. The average carbon (CO2-eq) emissions are 264.9, 37.0, and 67.9 t/ha/y−1 in Seoul, Chuncheon, and Gangneung, respectively. The annual carbon storage in the three urban green spaces (the amount of CO2-eq) is about 50% of the respective carbon emissions [22]. Lynch et al. believe that pruning, fertilization, pest control, and other works in green space maintenance can cause heavy carbon discharge. The design phase can directly influence the maintenance workload, such as the time investment, energy, and water consumption in urban green space [23].
2. Life cycle assessment of the environmental impact
2.1 Introducing of LCA
Life cycle assessment (LCA) is a comprehensive tool for evaluating the environmental impact of products or behaviors. This method can comprehensively analyze the potential environmental impact of human behavior from the beginning to the end by collecting the life cycle inventory (LCI) [24]. The LCA method includes four steps (Figure 3): goal and scope definition; analysis of life cycle inventory; environmental impact assessment; and interpretation of results [25]. It is mainly used to quantitatively study the negative environmental impacts (i.e., resource energy consumption and waste discharge) on the LCI list and seek ways to decrease the environmental stress of production or behavior system [26].
Figure 3.
The framework of LCA [24].
2.2 The development of LCA
LCA was initially applied primarily to research on resource consumption and environmental impacts of product packaging. In the early 1980s, due to the global energy crisis, environmental problems mainly focused on fossil energy consumption and combustion pollutant emissions, and the life cycle assessment method also entered the stage of academic discussion. At the same time, with the global solid waste problem that emerged from the late 1970s to the mid-1980s, the life cycle method has gradually become a resource analysis tool and has entered the field of scholars. Research at that stage mainly focuses on the assessment method construction, with limited case studies. The earlier LCA research was concentrated in the United States and encouraged by the government [27].
After entering the 1990s, LCA entered a stage of rapid development. In 1990, for the first time, the International Society of Environmental Toxicology and Chemistry (SETAC) hosted an international seminar on LCA. The concept of “life cycle assessment” was first presented at the conference. In the following years, the SETAC hosted and held several academic seminars and conducted extensive research on the theory and methods of life cycle evaluation [28]. Although the current life cycle assessment methodology still has many issues worth studying, the SETAC and the International Standards Organization (ISO) have been actively promoting the international standardization of LCA. The ISO 14040 standard (Environmental Management—Principles and Framework for Life Cycle Assessment) was promulgated on 1997, and the corresponding series of standards ISO 14041 (list analysis), ISO 14042 (impact evaluation), and ISO 14043 (interpretation of impact statements) are also in the following [24]. The standard system has a great improvement to the standardization steps of the LCA concept and the technical framework.
Construction of the LCI database is a vital factor in the development of LCA. LCI database includes the total environmental impact data on every life cycle stage of the upstream product. The LCI database construction starts from the early 1990s. Currently the word mainstream database includes “ecoinvent” in Europe and “Chinese life cycle database” (CLCD) in China [26].
2.3 The quantitative method of LCA
2.3.1 The general characterization model of LCA
Different ecological impact factors have different potential for the same type of environmental impact. Based on a certain ecological impact factor, the relative impact potential could be characterization [29]. Characterization is the main step to quantify the environmental impact intensity, which includes resource and energy consumption and waste discharge:
Consumption of resources and energy. Heat consumption is usually taken as a characteristic factor, and the material consumed in the system boundary is converted into a unified heat unit according to their energy consumption coefficients accumulated:
ECs=∑inαi×RCiE1
In the formula, ECs is the characteristic quantity of resource and energy consumption; take MJ as a characteristic index. RCi is the consumption of material i in a certain process of the system. αi is the equivalent coefficient of material i. At present, GB/T 2589-2008 standard offered majority kinds of materials in coal calorific equivalent coefficient.
Waste discharge. At present, a unified equivalent model has been established for the environmental impact of the LCA system on climate warming, environmental acidification, eutrophication, and environmental toxicity. The EIs of an environmental impact factor in the waste generated within the system boundary can be calculated by the following formula:
EIs=∑inβi×ECiE2
In the formula, ECi refers to the emission amount of factor i in waste discharge characteristic factors. βi is the equivalent coefficient of factor i. The coefficients of factors CO2, CH4, and N2O are 1, 21, and 310, respectively [30].
2.3.2 Standardization and weighted assessment of LCA characteristic result
Standardization refers to the ratio between the LCA characteristic quantity of an environmental impact factor and the regional total or average quantity of the factor, with the aim of eliminating the difference in dimension and series of each environmental impact factor. At present, data of energy and resources and emissions of environmental waste per capita in the world in 2000 are mostly used as standardized reference in the field of environment [31]. The calculation process is as follows:
REi=Ei/Si2000
In the formula, REi refers to the standardized result of environmental impact factor i. Ei is the LCA characteristic quantity of environmental impact factor i, including both EC and EI. Si(2000) refers to the world per capita standardized benchmark of environmental impact factor i in 2000.
The weighted assessment is based on the actual environmental load of each environmental impact factor to determine the weighted coefficient, which is used to revise the standardized results of LCA system:
WEs=∑inWi×REiE3
In the formula, WEs is the weighted value of environmental impact within the boundary of the LCA system. Wi is the weighted value of environmental impact factor i.
Standardized reference values and weight coefficients of two environmental impact factors, resource and energy consumption and climate warming potential (GWP), are shown in Table 1.
The characterization factors of environmental impact
Unit
The reference value of standardization unit/person [32]
Reference values and weight coefficients of some environmental impact characteristic factors.
2.4 The application of LCA on ecological research
In the environmental ecology research, LCA has been widely used in plant nursery, forestry management, and agricultural production. Lazzerini assessed the carbon emissions of two types of nursery plant cultivation (in-pot and on-field) in Tuscany (Italy). Guided by LCA, this study summarized the carbon emissions of farm structure, aboveground structure, input of cultivation, and packaging in nursery cultivation. He pointed out the GHG emission of in-pot cultivation was 7.4–26.5 kg CO2/m2/y−1, which was much higher than that of 0.6–1.0 kg CO2/m2/y−1 of on-field cultivation [34]. Berg summarized the energy consumption and carbon emissions in Sweden’s forestry management process by LCA. The forestry life cycle includes seedling production, silviculture, logging, and haulage to the wood processing plant. In Sweden forestry, the energy consumption (in m3 wood unit) is about 150–200 MJ/m3/y−1, and the carbon emissions (CO2-eq) is about 12.5–17.1 kg/m3/y−1. The energy consumption and carbon emissions in logging and transportation are the most obvious, accounting for more than 60% of the total amount [35]. Ingram used LCA method to study the management carbon footprint of red maple forest during planting. The life cycle of the study included 1-year seedling production and 4-year seedling field management. It was found that the carbon emission (CO2-eq) footprints were 2.9 kg/plant for tube feeding materials and the consumption of fuel and energy was 10.3 kg/plant during production, at a distance. In 386 km of transportation, 4.0 kg/plant and 3.3 kg/plant in planting and landscape sites, the most carbon emissions were from production to planting, accounting for 17.7 kg/plant and accounting for 86% of the total greenhouse gas emissions [36]. Haas et al. assessed the environmental impacts of intensive, extensive, and organic forage management in 18 grasslands in Allgau, Bavaria, and southwestern Germany by LCA. The energy consumption of tube feeding was 19.1, 8.7, and 5.9 GJ/ha/y−1, respectively, while the greenhouse gas emissions were 9.4, 7.0, and 6.3 t/ha/y−1, respectively. It was concluded that organic animal husbandry was more environmentally friendly and intensive animal husbandry had a stronger environmental impact [37].
At present, there are few studies on the environmental impact of urban green space using LCA. In 2015, Dr. Ji Yuan-yuan summarized the carbon emission inventory of landscape sites in the production, construction, maintenance, and abandonment stage. She believed that the main consumption material in maintenance stage includes fossil energy, irrigation water, fertilizer, and pesticides [38]. Strohbach and Haase believe that the total carbon emissions per hectare of urban green space in Leipzig (Germany) are about 2.6–4.7 t/CO2 in 50 years after its construction [39].
3. The LCA of urban green space maintenance
3.1 Goal and scope definition
The purpose of urban green space maintenance is to ensure the realization of landscape services. Therefore, the continuous supply of usability of green landscapes that meet the design requirements can be regarded as the “product” of maintenance work. Therefore, the environmental impact of the maintenance tasks can be defined as the goal of the green space maintenance LCA.
The maintenance of green space has long-term and repetitive characteristics. After the completion of the green space, the management work is continuously carried out. Although the content of the maintenance work will change with the growth of plants, the change is not obvious reflected in the annual period. Jiang Shipping divides the green space into three stages: initial age (≤3 years), middle age (4–10 years), and mature age (>10 years). It is considered that the annual management content of each stage is repeated [40]. Therefore, in the urban green space LCA evaluation, the life cycle of each stage green space can be carried out annually.
3.2 System boundary and LCI data collection
The system boundary is the evaluation scope of the LCA, and the material consumption and waste discharge within the system boundary are the substance list. When conducting LCA evaluation of products or behaviors, the related upstream and downstream processes are very intensive. Some process factors participate in system construction, but the environmental impact on the system is limited, or the environmental impact data is not clear. In order to avoid interference with the accuracy of the evaluation results, these processes are generally excluded from the system boundary. Figure 4 is a systematic flowchart of urban green space maintenance. The plant combinations of green space are divided into four layer subsystems of trees, shrubs, ground cover and turf based on the difference in maintenance work (Figure 5).
Figure 4.
The LCA system boundary of urban green space maintenance.
Figure 5.
The plant combinations in urban green space.
Figure 4 shows that the upstream of the system mainly contains the production and sales of the maintenance materials. This part of the list can be obtained by referring to the CLCD or by referring to the same LCA evaluation results. However, the upstream data is mostly the market average, and there may be large deviations [41]. In the system downstream, due to the different waste recycle ways taken by the different maintenance teams, the environmental impact list is difficult to obtain. Therefore, The LCA of green space maintenance system mainly includes on-site energy consumption and emissions. The list of this part comes from on-site investigation and has high reliability, which is also a direct reflection of the environmental impact of maintenance.
3.3 Characterization model of environmental impact in urban green space maintenance
Based on the general characterization model of LCA, using the equivalent coefficient of energy consumption and global warming potential (GWP) or climate warming potential, we establish an environmental impact characterization model of the maintenance material input and GHG emission inventory:
ECg=∑inαei×AwiE4
ECg refers to the characteristic quantity (MJ) of urban green space management resource and energy consumption. αei represents the resource and energy consumption equivalent coefficient of the species i list in the system. Awi refers to the input amount of the i substance in the system.
The calculation of the Awi value of petrol- and diesel-powered maintenance equipment can be obtained by the following formula:
Awi=∑anMwaEea×βaE5
where a is the maintenance equipment associated with the maintenance substance i in the system. Mwa refers to the workload of the maintenance equipment within the system boundary. Eea and βa represent the working efficiency and fuel consumption per time unit.
The calculation method of the GWP potential (kg/CO2) EIg of urban green space management is as follows:
EIg=∑inαci×Awi+EIegE6
αci is the GWP equivalent coefficient of the i input in the system. EIeg is the GWP characteristic quantity of the maintenance equipment used in the system boundary, which can be calculated by the following formula:
EIeg=∑anMwaEea×Aγa×Aαci+Bγa×Bαci+Cγa×CαciE7
Aγa, Bγa, and Cγa are the emission amount of climate warming factors CO2, CH4, and N2O in the system boundary, respectively. Aαci, Bαci, and Cαci refer to the equivalent coefficient of CO2, CH4, and N2O, respectively.
4. The quantification of environmental impact in urban green space maintenance
4.1 Introducing of research area
The research area of quantification of urban green space maintenance environmental impact was located in Zhengdong New District, Zhengzhou (China). The green coverage rate in research area is 49.1%. The construction of green space in the CBD area was completed in 2004, and it is a mature green area. The survey sites are (1) Hongbaihua Park with an area of 106,000 m2; (2) Zhengzhou Forest with an area of 264,000 m2; (3) Zhengdong New District Wetland Park with an area of 44,000 m2; and (4) No. 6 parking lot with an area of 39,000 m2. The plot area is 453,000 m2, accounting for about 60% of the total urban green area of the CBD (Figure 6). Thirty-four plant community samples of 20 m × 20 m were set in the research sites (Figure 7).
Figure 6.
The research sites in CBD area of city Zhengzhou. Resource: http://map.tianditu.com/
Figure 7.
The sample plots in research sites.
4.2 LCI data collection
The LCI data collection consists of two parts (2017.06–2018.07): (1) plant structure: the area (m2) of each plant layer in the sample survey site and the tree layer are calculated by the projected area of the canopy; (2) material input list: annual workload of each plant layer maintenance (trimming, irrigation, fertilization, pesticide, and plant waste removal). Table 2 shows the average amount of maintenance material inputs per ha of urban green space calculated according to the data collected in research samples. Table 3 shows the energy consumption and GHG emission of the maintenance equipment tested in the field.
Inventory of maintenance material
Units (U)
Woodland (U/ha/y−1)
Shrubs (U/ha/y−1)
Ground cover (U/ha/y−1)
Grassland (U/ha/y−1)
Petrol
kg
0
2 × 101
0
3.6 × 101
Diesel
kg
2.1 × 101
9.8 × 101
3.0 × 101
7.1 × 101
City water
m3
1.3 × 104
1.5 × 104
1.3 × 104
1.6 × 104
Fertilizer
kg
1.4 × 102
1.6 × 102
1.3 × 102
1.5 × 102
Pesticide
kg
1.0 × 101
2.7 × 101
1.1 × 101
4.5 × 101
Table 2.
Maintenance material input list in urban green space.
Equipment type
Energy type
Unit
Working efficiency/unit
Energy consumption (kg/unit)
GHG emission (kg/unit)
CO2
CH4
N2O
Hedge strimmer
Petrol
h
300 m2
0.60
1.69
8.96 × 10−3
3.20 × 10−4
Hand-driven mower
Petrol
h
300 m2
1.50
1.80
9.10 × 10−2
9.02 × 10−4
Riding mower
Petrol
h
2000 m2
2.30
2.68
3.74 × 10−3
5.40 × 10−4
3 m3 light pickup
Diesel
h
20 km
1.00
3.43
8.11 × 10−3
5.22 × 10−4
5 m3 light lorry
Diesel
h
20 km
2.60
6.20
1.81 × 10−3
9.39 × 10−4
Table 3.
Energy consumption and GHG emission inventory of maintenance equipment.
4.3 The LCA result of environmental impact in urban green space maintenance
Environmental impact characteristics of each plant layer in mature green space maintenance.
Plant layer
Environmental impact factor
Weighted environmental impact index (ha/y−1)
Trimming
Irrigation
Fertilization
Pesticide
Waste transport
Total
Woodland
Resource and energy consumption
0
1.33 × 10−3
4.80 × 10−4
6.26 × 10−5
3.82 × 10−5
1.91 × 10−3
GWP potential
0
0
3.70 × 10−3
6.30 × 10−5
9.24 × 10−4
4.68 × 10−3
Sum
0
1.33 × 10−3
4.18 × 10−3
1.26 × 10−4
9.62 × 10−4
6.60 × 10−3
Shrubs
Resource and energy consumption
3.66 × 10−5
1.56 × 10−3
5.31 × 10−4
1.65 × 10−4
1.78 × 10−4
2.47 × 10−3
GWP potential
1.15 × 10−3
0
4.09 × 10−3
1.66 × 10−4
4.30 × 10−3
9.71 × 10−3
Sum
1.19 × 10−3
1.56 × 10−3
4.62 × 10−3
3.32 × 10−4
4.48 × 10−3
1.22 × 10−2
Ground cover
Resource and energy consumption
0
1.40 × 10−3
4.53 × 10−4
6.81 × 10−5
5.47 × 10−5
1.97 × 10−3
GWP potential
0
0
3.49 × 10−3
6.85 × 10−5
1.97 × 10−3
5.53 × 10−3
Sum
0
1.40 × 10−3
3.94 × 10−3
1.37 × 10−4
2.03 × 10−3
7.50 × 10−3
Grassland
Resource and energy consumption
6.61 × 10−5
1.75 × 10−3
5.07 × 10−4
2.72 × 10−4
1.28 × 10−4
2.72 × 10−3
GWP potential
1.15 × 10−3
0
3.91 × 10−3
2.74 × 10−4
4.67 × 10−3
1.00 × 10−2
Sum
1.22 × 10−3
1.75 × 10−3
4.41 × 10−3
5.46 × 10−4
4.79 × 10−3
1.27 × 10−2
Table 5.
Weighted environmental impact index of each plant layer in mature green space.
\n',keywords:"urban green space, plant community maintenance, environmental impact, energy consumption, GHG emissions",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/70065.pdf",chapterXML:"https://mts.intechopen.com/source/xml/70065.xml",downloadPdfUrl:"/chapter/pdf-download/70065",previewPdfUrl:"/chapter/pdf-preview/70065",totalDownloads:168,totalViews:0,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,dateSubmitted:"May 29th 2019",dateReviewed:"October 4th 2019",datePrePublished:"November 17th 2019",datePublished:"December 16th 2020",dateFinished:"November 17th 2019",readingETA:"0",abstract:"As a fundamental part of the urban function, urban green space faced a long-term maintenance requirement. The maintenance of urban green space (i.e., trimming, irrigation, fertilization, pesticide, and plant waste removal) can have environmental impacts, such as energy consumption and greenhouse gas (GHG) emission. This chapter focuses on the adjustment of the plant communities’ combinations in urban green space to reduce the environmental impacts in long-term maintenance. The plant communities in urban green spaces are a combination of four plant layers: woodland, shrubs, herbicides, and grassland. In this chapter, we will start to investigate the environmental impacts in the maintenance of urban green space. Then we introduced the quantitative method life cycle assessment (LCA), to quantify the environmental impacts of the maintenance tasks. We analyzed the maintenance environmental impact (MEI) index of 95 plant community samples (20 m × 20 m) in Zhengzhou (China) through LCA and sorted out the changing curves of the MEI index during the change of the combined amount in each plant layers. Finally, we sorted out the MEI strength of the plant layers and summarized the low MEI plant community model. The low MEI model can save energy consumption and GHG emissions of the maintenance tasks, to contribute to the sustainable development of the urban green space.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/70065",risUrl:"/chapter/ris/70065",book:{slug:"sustainability-in-urban-planning-and-design"},signatures:"Ning Li and Yang Liu",authors:[{id:"306585",title:"Dr.",name:"Yang",middleName:null,surname:"Liu",fullName:"Yang Liu",slug:"yang-liu",email:"kelivnliu@163.com",position:null,institution:null},{id:"312405",title:"Prof.",name:"Ning",middleName:null,surname:"Li",fullName:"Ning Li",slug:"ning-li",email:"530273516@qq.com",position:null,institution:null}],sections:[{id:"sec_1",title:"1. The environmental impact in urban green space maintenance",level:"1"},{id:"sec_1_2",title:"1.1 The fast expansion of maintenance workload in urban green space",level:"2"},{id:"sec_2_2",title:"1.2 The maintenance tasks in urban green space",level:"2"},{id:"sec_3_2",title:"1.3 The energy consumption and emission discharge in green space maintenance",level:"2"},{id:"sec_4_2",title:"1.4 The literature review of environmental impact in urban green space maintenance",level:"2"},{id:"sec_6",title:"2. Life cycle assessment of the environmental impact",level:"1"},{id:"sec_6_2",title:"2.1 Introducing of LCA",level:"2"},{id:"sec_7_2",title:"2.2 The development of LCA",level:"2"},{id:"sec_8_2",title:"2.3 The quantitative method of LCA",level:"2"},{id:"sec_8_3",title:"2.3.1 The general characterization model of LCA",level:"3"},{id:"sec_9_3",title:"Table 1.",level:"3"},{id:"sec_11_2",title:"2.4 The application of LCA on ecological research",level:"2"},{id:"sec_13",title:"3. The LCA of urban green space maintenance",level:"1"},{id:"sec_13_2",title:"3.1 Goal and scope definition",level:"2"},{id:"sec_14_2",title:"3.2 System boundary and LCI data collection",level:"2"},{id:"sec_15_2",title:"3.3 Characterization model of environmental impact in urban green space maintenance",level:"2"},{id:"sec_17",title:"4. The quantification of environmental impact in urban green space maintenance",level:"1"},{id:"sec_17_2",title:"4.1 Introducing of research area",level:"2"},{id:"sec_18_2",title:"4.2 LCI data collection",level:"2"},{id:"sec_19_2",title:"4.3 The LCA result of environmental impact in urban green space maintenance",level:"2"}],chapterReferences:[{id:"B1",body:'National Bureau of Statistics. Statistical Yearbook of the Republic of China. 2019'},{id:"B2",body:'Sun Z. Study of the urban landscape greening sustainable development measures in the conservation-oriented society. Chinese Landscape Architecture. 2007;9:15-21'},{id:"B3",body:'Yajun W. 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Landscape & Urban Planning. 2012;1(104):95-104'},{id:"B40",body:'Jiang SP, Peng YL. Study on maintenance and management for residential planting. Journal of Chinese Landscape Architecture. 2003;19(3):29-32'},{id:"B41",body:'Liang L, Chen YQ, Gao WS. Integrated evaluation of circular agriculture system: A life cycle perspective. Environmental Science. 2010;31(11):2795'}],footnotes:[],contributors:[{corresp:null,contributorFullName:"Ning Li",address:null,affiliation:'
Henan Agricultural Landscape Planning and Design Institute, China
College of Forestry, Henan Agricultural University, China
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1. Ionic state of indium in perchlorate solutions
It is known that perchlorate ion does not form complex compounds even with extremely strong complexing metal ions [1]. The difficulty in preparing perchlorate metal complexes is the lack of suitable solvents. Water molecules and most non-aqueous donor media displace such a weak ligand as the ClO4− ion from the inner sphere of the compound. The formation of a coordination bond between the perchlorate ion and the complexing cation is possible only in acceptor or very weakly donating solvents. The successful synthesis of perchloro-complexes in work [2] is associated with the use of anhydrous perchloric acid as a reaction medium.
These fairly well known provisions are fully confirmed for indium perchlorate, which is proved by various research methods [3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19]. The absence of coordination interaction of acid ions in the “In3 + - ClO4−– H2O” system is indicated by the spectra of Raman scattering [5, 6, 7, 8, 9, 10, 11]. IR spectra [12] including near infrared [13, 14, 15] and spectroscopy of disturbed total internal reflection [13, 16], NMR signals [17, 18]. However, partial formation of ion pairs between them is allowed [8, 18].
In the Raman spectra of the perchlorate solution, only the lines of the ClO4− anion and the aquocomplexes of the In3 + ion ⋅aq were found [6]. Raman and IR spectroscopic studies of indium hydration in perchlorate solutions revealed octahedral hexaaquocation [In(H2O)6]3 +. According to the data of the Raman spectra, the aquocomplex is stable in acidic perchlorate solutions, and in the studied concentration range, neither inner sphere nor hydroxostructures are formed [9].
There is no evidence of the complexing effect of the highly concentrated electrolyte NaClO4 1.1÷9.1 M and by electrophoresis [19]. Spectrophotometrically in the ultraviolet region of the spectrum, there were no significant signs of direct interaction in aqueous solutions of In(ClO4)3 salts [20]. Also, no intrinsic complexation influencing the activity of In3+ was reliably detected up to a sodium perchlorate concentration of 16 mol/kg [19, 21] and with an In(ClO4)3 content of more than 4 M [6, 9].
Similar results, denying the likelihood of coordination interaction of In3+ with ClO4−, were obtained when studying the solvation of cations by NMR on H1 and P31 nuclei in aqueous-organic mixtures [22].
The proton-magnetic resonance measurement of the coordination number of perchlorate water-organic systems testifies to the six fold coordination of water molecules around the indium cation and to the absence of strong evidence of contact ion pairing [23, 24]. It was not possible to detect the binding of indium to perchlorate ions ClO4− by special experiments carried out in mixed water-non-aqueous mixtures and organic media [25].
The absence of complex compounds of indium with perchlorate ion is also indicated by the data of liquid extraction, in particular, three n-octylamine does not extract indium from a solution with an HClO4 concentration less than 2 M [4]. At the same time, from concentrated solutions of perchloric acid for cationic reagents - alkylphosphoric acids (for example, di-2-ethylhexylphosphoric acid; Figure 1) - a possible extractable form of indium compounds is the complex cation [InClO4]2+ [26]. It is also assumed that during the extraction of indium in aqueous solutions of hydrochloric acid at its various concentrations and constant ionic strength maintained by the addition of perchloric acid, indium is present in the organic phase in the form of ionic aggregates HClO4⋅HInCl4 [27]. The latter formation is possibly caused by the coextractability of perchloric acid due to its higher extraction affinity as compared to hydrochloric acid. In the aqueous phase, there are only chloride complexes, which are subjected to extraction with various oxygen-containing solvents.
Figure 1.
Extraction of III subgroup metal ions with di (2-ethylhexyl) phosphoric acid depending on the concentration of perchloric acid: 1 - Ga (III), 2 - In (III), 3 - Tl (III) [26].
The likelihood of the formation of perchlorate and mixed-ligand complexes also applies to extraction systems based on 4-methyl-2-pentanone and 4-methyl-2-pentanol, the extractable forms of which are compounds of the composition [In(ClO4)3], [InHal(ClO4)2], [InHal2(ClO4)], where bromine, iodide, or thiocyanate ion is present as the halide and pseudohalide of the ligand. The aqueous phase is characterized by a constant ionic strength of 4.0 due to the salt background of sodium perchlorate and salts of NaBr, NaJ or NaSCN of variable concentrations. The role of NaClO4 in liquid distribution is reduced not only to a change in the activity and composition of the solution, but also to the extraction of ion pairs of charged indium complexes, which greatly increases in the presence of perchlorate ions [28].
An example of the special effect of perchlorate ion on the extraction behavior of indium (III) is its interaction in a mixture of extractants 1-phenyl-3-methyl-4-acylpyrazol-5 (PhMAPr) with tri-n-phosphine oxide (TOPhO) in toluene [29] and PhMAPr with a base salt — Aliquat-336 [29]. If the reaction of interfluid distribution in a perchlorate medium proceeds according to the equation (1):
and from aqueous solutions of H(Na)Cl, ClO4 during extraction with a mixture PhMAPr and TOPhO have a synergistic effect and the process is described by the equation (2):
where n = 0–3, then in the case of perchlorate salt Aliquat-336, this phenomenon is not observed due to its finding in the form of R4N+ClО4−, although when using in the same system high-molecular-weight ammonium in chloride and nitrate forms, the effect of synergism is not only preserved, but also increased.
When studying the coordination properties of polyvalent metal ions, including indium, by titrimetric and ion-exchange methods, only weak signs of complexation in perchloric acid were noted [30].
The cation-exchange behavior of indium (III) ions in the presence of perchloric acid and an organic solvent in the form of methyl alcohol and acetone also indicates the absence of fundamental changes in the ionic state of indium in such a sorption system. Both in the presence and in the absence of these solvents, the indium ion interfacial distribution indices in the perchloric acid medium are higher than in the hydrochloric acid medium (picture 2) [31]. Thus, if the coordination properties of such acid ligands as halides, sulfate, thiocyanate [32], and to some extent nitrite [33] in aqueous-organic mixtures can be activated, which leads to the formation of more acid-saturated complexes, then the perchlorate ion under these conditions in relation to indium, as a complexing agent, remains very passive (Figure 2).
Figure 2.
Dependence of the distribution coefficients of indium in 0.1 M HClO4 (1.3) and 0.1 M HCl (2, 4) on the content of the organic solvent: 1 and 2 - methanol; 3 and 4 - acetone [31].
From other alternative points of view, attention is drawn to the study of the effect of the salting-out electrolyte on the distribution coefficient of indium during the extraction of its tenoyl-three-fluoroacetonate complex with benzene from aqueous perchlorate solutions, where the presence of complexation of indium with the perchlorate ion was confirmed.
The revealed relationship between the salting-out parameter and the stability of indium complexes with various anions formed in the aqueous phase indicates that the strength of the acidic complexes by the nature of the ligand changes in the series of salts: NaCl > > NaNO3 > NaClO4 [34].
A characteristic feature of indium perchlorate solutions, like other indium salts, is the extremely high viscosity of aqueous solutions of In(ClO4)3, due to the increased degree of hydration of the three-charged indium ion [6]. A simple substance with the composition In(ClO4)3 ~ 8H2O crystallizes from concentrated aqueous solutions of indium perchlorate [11], and in dilute perchloric acid, indium is in the form of the cation [In(H2O)6]3+.
2. Study of ion hydration by the method of electrical conductivity in the system
“In(ClO4) 3 - HClO4– H2O” shows that the total number of water molecules oriented by the cation is nIn3+ = ~ 9, which includes water molecules that make up the near and far environment of the cation. The decrease in nIn3+ relative to the maximum value equal to 12 reflects the approach of the hydration and anionic environment of indium to what is characteristic of crystalline hydrates, and indium perchlorate crystallizes from an aqueous solution with eight water molecules. In the series of cations ΙΙΙ of the Al3+-In3+ subgroup, there is a tendency to a decrease in nMes+ with an increase in the crystal chemical radius. The reason for this is the decrease in the polarizing ability of the cations. Consequently, this leads to a weakening of the bonds of near and outer-sphere water molecules with a probable increase in the residence time of anions near the [Me(H2O)6]3+ cation [35].
The solubility of indium perchlorate salt at 0° and 25°C is 3.23 and 3.53 mol/kg H2O, respectively. More accurately speaking about the macroscopic properties, about the possible composition of crystalline hydrates precipitating into the bottom phase, about the processes preceding crystal formation, allow the polytherms of solubility [36]. Their analysis shows that there is a qualitative similarity in the solubility polytherms of the aluminum subgroup perchlorates. The value of the molar fraction of water unbound to salt in the eutectic for perchlorates is constant (Nw = 0.94 ± 0.1). The freezing temperatures of eutectic compositions are close to −28 ÷ −31°С and all curves have an inflection - a maximum that corresponds to the existence of a chemical compound. In the case of indium perchlorate, this is a 28-aqueous crystalline hydrate. In addition, after reaching the concentration of 2.8 mol/kg H2O, the phenomenon of glass transition of this solution is observed. However, the position of the eutectic concentration on the solubility polytherm depends not so much on the nature of the cation as on the number of water molecules that are part of the crystalline hydrate. The reason for the existence of compounds enriched with water in the eutectic should be sought in the fact that the stable bridges formed as a result of local hydrolysis (cation ··· ОН− ··· Н3О+) are able to retain a large amount of water. Thus, providing the possibility of the formation of high-water crystalline hydrates at temperatures below 0°C. However, as the solution concentrates, structurally forced processes begin. Rearrangement of one dominant structure into another containing a smaller number of water molecules in the cybotactic group. These processes are accompanied by glass transition (Figure 3).
Figure 3.
Perchlorate solubility polytomes: (a) Al (ClO4)3, (b) Ga (ClO4)3, (c) In (ClO4)3 [36].
The structure of aqueous solutions of indium perchlorates and the state of water were studied by IR spectroscopy in the region of the first overtone of water (NIR spectra) using chemometric analysis to the concentration dependences of the spectra. It is noted that hydrolysis occurs in indium (III) perchlorate solutions, and due to the high enthalpy of hydration of In3 +, exclusively solvate-separated ion pairs are formed. In other words, the formation of complexes of the composition In3+ (Н2О) n (ClO4)− occurs, where n = 1–2 with a decrease in the symmetry of the ClO4− ion: Тd → C3v → C2v with an increase in the concentration of indium in solutions acidified with perchloric acid [14, 15].
Perchlorate ion has the shape of a regular tetrahedron. Its hydration shell consists of eight water molecules. The distribution of these shells around the ClО4− ion is uniform. Presumably, it is low hydrating capacity [37].
Indium perchlorate salt is a hygroscopic substance readily soluble in water and it can be obtained by dissolving indium metal in perchloric acid at a moderate temperature. Its anhydrous modification crystallizes because of the interaction of silver perchlorate and indium chloride in a methanol solution. There are also several forms of indium hydroxopochlorates, which are precipitated in their solutions in the presence of sodium perchlorate [38]. At pH 4.82, a salt of the composition In4OH(ClO4)11 was isolated, at pH 3.77 - In2OH(ClO4)5, and in the pH range 2.56–3.14 - In4(OH)3(ClO4)9.
Determination of the apparent ionic volumes of particles by measuring the density of indium (ΙΙΙ) perchloric acid solutions showed [39] that, depending on the degree of dilution, the formation of a compound of the composition [In(H2O)5ClO4]2+. However, there are no convincing reasons to consider the possible entry of the perchlorate ion into the inner sphere of the indium aquion.
According to X-ray diffraction data, the structure of a hydrated indium ion (ΙΙΙ) in a 3 M aqueous solution of perchlorate is an aquo-complex, in which the first hydration shell contains six water molecules with a bond length of 2.15 ± 0.03 Å between In3+ and nearby H2O [40].
To establish the structure of trivalent indium perchlorate, the crystalline salt was obtained by dissolving indium (III) oxide in an equimolar amount of perchloric acid on heating– [In(Н2О)6](ClO4)3. By isothermal evaporation at room temperature from an aqueous solution of In In(ClO4)3, crystals [In(Н2О)5](ClO4)3 unstable in air were isolated. X-ray structural analysis of two forms of indium perchlorate - [In(Н2О)6](ClO4)3 and single crystal [In(Н2О)6](ClO4)3⋅3H2O indicates that both these structures are formed by hexaaquocation [In(Н2О)6]3+ and perchlorate ions. In this case, [In(Н2О)6](ClO4)3⋅3H2O contains crystallization water molecules. But the structure of [In(Н2О)6](ClO4)3 is cubic, and [In(Н2О)6](ClO4)3⋅3H2O is rhombic, each of them with the corresponding definite geometric parameters, in which the aquated indium complexes are close to the ideal octahedron. Special attention should be paid to the hydration state of indium perchlorates. In all likelihood, the hydration composition of its salt is not eight, but nine-water, consisting of six-coordinated water molecules and three crystallization ones. At the same time, the existence of a six-water modification unstable in air that does not contain molecules of crystallized water is possible. However, since the compound is highly hygroscopic, it is possible that partial dehydration occurs in the processes of pre-preparation of samples for chemical analysis [In(Н2О)6](ClO4)3⋅3H2O [41].
The available X-ray diffraction measurements carried out for perchlorate solutions of indium (ΙΙΙ) at temperatures from 25 to 250° C under water vapor pressure indicate that the distance In3+ − oxygen (water) in the octahedral configuration of the aqua complex remains constant and equal to 2.14 ± 0.01 Å. In 1.0 M HClO4 solutions, the formation of the ion pair In3+ − perchlorate [InClO4(H2O)5]2+ is observed, in which the distance In3+ − chlorine (perchlorate) changes from 3.14 to 3.12 Å with an increase in temperature to 250° С. At the same time, no noticeable destruction of the octahedral hydration shell of the aqua-ion of indium at temperatures up to 300° C was recorded [42].
In addition to the crystalline hydrate of the composition In(ClO4)3⋅8H2O, isolated from an aqueous solution, the corresponding dimethylforamide solvate In(ClO4)3⋅6(CH3)2NCHO was isolated by the preparative method of double recrystallization due to the solvation effect caused by the peculiarities of the chemical interaction of indium ions with molecules of an organic solvent [43].
The anhydrous salt of indium (III) perchlorate is obtained in the course of the exchange reaction between InCl3 or InJ3 with AgClO4 in methanol solution [44].
Sequential thermal dehydration of indium perchlorate heptahydrate leads to the decomposition of the salt, the final product of which is indium trioxide [45].
When studying the effect of the composition and concentration of the water-salt system on the EMF of the cell Hg(liquid)//Hg2Cl2(solid.)/NaCl(saturated.)/NaAni//Ме(ClO4)n, In(ClO4)3/In(solid.), где Меn+ = Li, Na, Mg; NaAni = 5416 M NaCl, 4,0 M NaNO3, 3,72 M and 6,72 M NaClO4 it was shown that the nature of the salts that form the salt bridge and their amount have a definite effect on the EMF of the cell. The greatest difference in the EMF values was noted when comparing the units of 4.0 M NaNO3 and 6.72 M NaClO4, and in the case of 3.72 M NaClO4, the values are very close. The chemical composition and concentration of the salt background have the greatest effect on the emf and the activity coefficient of the In3 + cation (γ ±): the γ ± values rapidly increase (by 5–6 orders of magnitude) with a change in the magnesium salt content from 0.5 to 4 M and up to 13 M sodium salts. Depending on the nature of the salt background, γ ± is ranked in the order Mg(ClO4)2 > LiClO4 > NaClO4 [21].
IR spectroscopy of the synthesized series of compounds of the cationic type [In(Lig)n](ClO4)3, when n = 6, 4, 3, and 2, and the ligands are urea, dimethyl sulfoxide, Ph3P, Ph3PO4, 2,2′-Dipy, En, 2,2,2′-three-pyridyl and others, indicates that the perchlorate ion is a part of the anionic part of the complex structure [46]. By means of an exchange reaction in acetone solutions, hexa aqua salt [In(H2O)6] (ClO4)3 under the action of dimethyl sulfoxide or dimethylformamide is easily converted into solvates [In(DMSO)6](ClO4)3 and [In(DMFA)6](ClO4)3 [47]. Subsequently, X-ray structural studies established the structure of the crystal complex of indium hexa (dimethylsulfoxide) perchlorate (ΙΙΙ) [In(ДМСО)6](ClO4)3 [48].
Thus, there are clearly no compelling reasons to consider the existence of complexes of indium with perchlorate ion, especially its anionic forms, as possible, and as a consequence, the indium ion in such a medium is a simple hydrated cation. Apparently, under certain conditions, it is possible to admit the formation of ion pairs, where the perchlorate ligand is localized in the outer sphere with respect to the central atom, i.e. attached to all aquo-ion.
Therefore, in the practice of studying the complexing properties of indium, as well as most other metal ions, salt perchlorate and perchloric acid are traditionally used to create a given ionic strength of a solution and as a source of acid anions that do not form complexes. And also in those cases when it is necessary to assess the interaction of cations, for example, with water, not complicated by the formation of their acidic complexes.
The macro-properties of aqueous solutions of electrolytes of the gallium subgroup are significantly influenced by the peculiarities of the interaction of metal cations with water. The regularities of changes in such characteristics as the bulk properties of perchlorate solutions, isobaric expandability, adiabatic compressibility and heat capacity (isobaric and isochoristic) [49, 50] were analyzed from the point of view of the specificity of reactions of metal cations with dipoles of water molecules, depending on their electronic structure p- and d-metals of the third group [51].
It is quite natural that the studied macroproperties change nonmonotonically in the gallium subgroup. In this case, the type of non-monotony corresponds to the unequal sensitivity of each property to one or another result of interaction with water. It can be seen from Figure 4 that when passing from the dependences ∆Fк to the dependences ∆V, ∆FE and ∆Ср, the direction of the break in the Ga – In – Tl line gradually changes to the opposite. It follows from this that the ratio of the factors of water binding and its polarization is different for different properties. The factor of water binding predominates in the influence of the ∆Fк compressibility, which leads to the appearance of a rather sharp maximum on the “∆Fк - NGa-In-Tl” contour at the point of the least vigorously hydrated indium ion. In the case of the characteristics of the specific volume ∆V, the effect of compression of the bound water is partly compensated by the formation of openwork outer-sphere associates, as a result of which the maximum on the ∆V curve disappears.
Figure 4.
Dependence of changes in macro properties during the formation of perchlorate solutions on the hydration characteristics of group III cations: 1 - Δ(Ср - Сv) (1.0 M solutions) (Cp and Cv isobaric and isochoric heat capacities); 2 - ΔV (specific volume); 3 - ΔFE (expandability); 4 - ΔFC (compressibility); 5 - ΔCr (0.5 M); 6 - log β1 (β1 is the constant of the 1st stage of cation hydrolysis); 7 - ΔНr (enthalpy of hydration of the cation); 8 - ΔSr (entropy of cation hydration) [51].
The course of the dependence “∆FE - NGa-In-Tl” is antibate to the curve “∆Fк - NGa-In-Tl”, which may, firstly, be a consequence of the unequal degree of compaction of water molecules during hydration, and the greater the degree of compaction, the more ∆FE, and, secondly, is due to different degrees of water polarization and localized hydrolysis of cations. Finally, the dependence “∆Ср - NGa-In-Tl” demonstrates the absolute predominance of the effects of water polarization and localized hydrolysis over the influence of differences in the degree of water binding by cations, since the last of these factors should have caused the reverse course of the curve. Such a significant positive effect of water polarization and localized hydrolysis on heat capacity is apparently caused by corresponding changes in the set of frequencies of intra- and intermolecular vibrations of the aqua complex as a result of polarization, as well as redistribution of “O – H” bonds and hydrogen bonds due to local hydrolysis.
The comparisons made refer to the region of relatively dilute solutions. With an increase in concentration, the pattern of changes in properties from subgroup to subgroup, as well as within the subgroup, changes. For example, in Figure 5 dependences “∆V - NIII” for the subgroup of gallium and scandium change places with increasing salt concentration. This is probably because at low concentrations the ∆V values reflect largely the change in the volume of the outer-sphere water, and at high concentrations, the water in the inner coordination sphere of cations.
Figure 5.
Dependence of changes in specific volume during the formation of solutions perchlorates with concentration, mol/dm3: 1–0.1; 2–0.5; 3–1.0; 4–3.0 by nature trivalent cations [51].
Comparison of the tendencies of changes in the bulk properties of solutions from concentration Figure 5, apparently, show that the relative compression of the outer-sphere water is greater for d-metal ions and the compression of water in the inner sphere is, on average, greater for p-metal ions.
In concentrated solutions, the regularities of changes in properties in both groups depend mainly on the state of water in the inner sphere: in the subgroup of d-elements - on the degree of its compression, and in the subgroup of p-elements - on the degree of attraction and polarization. In dilute solutions, an important role is played by the state of the outer-sphere water, namely the degree of its destruction or, conversely, structuring. However, if, in the p-subgroup, the structuring of the outer-sphere water is more typical, and for the d-subgroup, destructuring is most likely [51].
The viscosity and density of perchlorate solutions are significantly influenced by the ability of cations to hydrate. The increased relative kinematic viscosity and the relative activation energy of the aqueous flow of solutions of aluminum, gallium and indium perchlorates is obviously a consequence of the formation of a hydration shell with a branched network of very strong hydrogen bonds by the cation. Within the gallium subgroup, the positive hydration of the ion is expressed the weaker, the larger its radius [52].
In this case, although the anion is not an indifferent component, its nature does not play a particularly important role in the nature of changes in the macro-properties of solutions, since the perchlorate ion has an approximately equal effect on the destruction of the primary structure of water in all systems. The only exceptions are Tl(ClO4)3 solutions, where the formation of outer-sphere ionic associates with hydrated thallium (ΙΙΙ) cations is evident [51].
From the analysis of the compensation spectra of the multiply disturbed total internal reflection, it follows that according to their destructive effect, the anions are arranged in a row ClO4− > NO3− > > Cl−, and for sulfocation it is not found at all. The formation of a covalent bond “water cation” leads to the strengthening of H-bonds in water, and in the case of solutions of triple-charged cations, additional stabilization of the water structure takes place, which complicates the process of destruction of hydrogen bonds even with such a strongly destructive anion as perchlorate [16].
The interrelation between the formation of outer-sphere water associates and the phenomenon of hydrolysis is especially evident from the comparison of the heat capacities of perchlorates in the series of triply charged cations of metals of the gallium subgroup with the values: 6 - lg β1 (β1 is the constant of the 1st stage of hydrolysis of the cation); 7 - ΔНr (enthalpy of hydration of the cation); 8 - ΔSr (entropy of cation hydration) [51, 53, 54] where the polarizing effect of cations on water makes the greatest contribution to the heat capacity even in dilute solutions. All this, moreover, agrees with the results of studying the vibrational spectra of solutions of gallium and indium perchlorates, showing that the water molecules surrounding these ions are polarized not only in the first, but also in the second coordination layer, thus the fraction of polarized water molecules in these solutions is unusual. But high, their contribution to the heat capacity of the solution is also significant [55]. Thallium (III) perchlorate solutions have the highest heat capacity, but here it should be noted that the reason for this in this case may be not only water polarization and local hydrolysis, but also the tendency of Tl3+ ions to form perchlorate complexes [56].
The form of the dependences of the apparent molar heat capacity of the PS P2 of group III metal perchlorates on the salt concentration deviates from the rectilinear, especially for La(ClO4)3 and Tl(ClO4)3Figure 6a. The regularities of changes in PS P2 are also explained in the light of ideas about the energy of interaction of ions with water, the state of water in hydration shells, and the effect of ions on the structure of water. In the gallium subgroup, the role of another factor, the hydrolysis of aquocations, increases significantly. Probably, the point for Ga(ClO4)3 owes its higher position to hydrolysis as compared with indium in Figure 6b [49].
Figure 6.
Dependence of the apparent molar heat capacity of metal perchlorates (Ps) (a, b) [49] and the heat capacity due to outer-sphere interactions of ions (ΔC) (c) ([53], p. 266), on the concentration: 1 - Al(ClO4)3, 2 - In(ClO4)3, 3 - Sc(ClO4)3, 4 - Ga(ClO4)3, 5 - La(ClO4)3, 6 - Y(ClO4)3, 7 - Tl(ClO4)3, 8 and 9 МеIII(ClO4)3–0.1 m, 10–0.5 m, 11–3.0 m.
Of the entire sum of contributions to the total change in the heat capacity of dissolution of perchlorates, the greatest effect of the specific nature of cations on the heat capacity of solutions occurs through the outer-sphere interactions (ΔСV). As you can see (Figure 6b). for the considered types of electrolytes in a significant range of concentrations ΔС are negative, which may be due not only to the outer-sphere hydration of ions, but also to their destructive effect on a certain part of the outer-sphere water. It is not yet possible to separate these two effects. However, at high concentrations, the sign of ΔCV hanges to the opposite, indicating, apparently, an increase in the role of the effect of outer-sphere aqueous, as well as ion-ion associates ([50], p. 266).
The recorded changes in the bulk properties of perchlorates of the aluminum subgroup from their concentration are also associated with the individual nature of the interaction of ions with water and among themselves. The densities of Al(ClO4)3, Ga(ClO4)3 In(ClO4)3 solutions at temperatures of 24, 25, and 27° C, the speed of sound, specific adiabatic compressibility and isobaric expandability in the concentration range from 0.1 m to saturation, and the shape dependences of apparent molar volumes (FV), compressibility (FК) and expandability (FЕ).
As follows from Figure 7 the values of FV and compressibility FК monotonically increase with an increase in the electrolyte concentration, but the FV for Al(ClO4)3 - decrease, and in the case of Ga(ClO4)3 and In(ClO4)3, in all likelihood, pass through a maximum. The dependences of FV on m½ are straightforward, and FK are curvilinear and for different cations they differ from each other both in their position and in the angle of inclination. The profile of the expansibility curves of PU differs greatly from the characteristics of volumes (FV) and compressibility (FK), including the sequence of arrangement of metal ions [49, 50].
Figure 7.
Dependence of: a – apparent molar volumes (FV), b – compressibility (FК) and c – expandability (FЕ). From mperchlorates: 1 - Al(ClO4)3, 2 - Ga(ClO4)3 3– In (ClO4)3 [49].
The influence of the coordination number on the compressibility of cations is, of course, due to the fact that the coordination water in the first layer practically loses its compressibility. The fact of compressibility manifests itself rather through external-sphere water than through coordination water. This is probably why the hydration numbers of cations, calculated from the compressibility data, turn out to be higher than their c.n. The data are reflected in the Table 1, which also shows the change in the isochoric heat capacity of similar electrolytes [53].
Electrolyte
Coordination number of cations
“Acoustic” hydration number
Change in isochoric heat capacity –ΔСV2 (J/K⋅mol) upon dissolution of subgroup III metal perchlorates on concentration (m)
0,5 m
1 m
2 m
3 m
4 m
Al(ClO4)3
6
12,4
411
373
296
223
Sc(ClO4)3,
6
11,3
383
327
248
195
151
Ga(ClO4)3
7–8
12,5
343
290
233
186
144 (3,83 m)
Y(ClO4)3
6
13,2
320
276
211
163
114
In(ClO4)3
6
11,0
345
322
257
205 (3,19 m)
Tl(ClO4)3
6
13,4
116
Table 1.
Change in isochoric heat capacity.
The correlation between the polarizing forces of the cation (P) and the eutectic concentration of aqueous solutions of perchlorates (Figure 8) indicates that the higher the value of the polarizing force, the stronger the cation interacts with water molecules. Therefore, due to the greater polarizing force of the cations of the gallium subgroup, which characterizes the state of the “cation - water” bond, there is a significant destruction of the intrinsic structure of water and an increase in the number of water molecules drawn from the solution into the sphere of influence of the cation [13].
Figure 8.
Correlation of the polarizing forces of cations (P) and the eutectic concentration (meut) of aqueous solutions of group III perchlorates MeIII(ClO4)3 ([50], pp. 124–126).
In addition to indium perchlorate salts, for elements of the aluminum subgroup, their iodates МеΙΙΙ(JO3)3⋅nH2O, are also known, including indium iodate with the composition In(JO3)3⋅2H2O [57, 58]. In contrast to perchlorate, indium iodate is characterized by a low degree of solubility, which in water at a temperature of 25° C is ~0,05% by weight (logSP = 2.5), and slightly more passes into solution under the action of nitric acid, showing the maximum value of solubility equal to 16.9 g/dm3 at a concentration of 300 g/dm3 HNO3.
Indium (III) is quantitatively precipitated from the solution in the pH range 1.9–7 with sodium (potassium) periodate with the formation of a precipitate corresponding to formula In5(JO6)3, the composition of which is constant at a temperature of 120–270° C. The crystalline compound of indium paraperiodate is slightly soluble in water, and respectively, in 1%, 0.3% and 0.5–1% carbonate, nitrate and ammonium acetate, but it is readily soluble in dilute mineral acids. The solubility of indium paraperiodate in water at 20° C is 6,4⋅10−4 g-mol/dm3 or 7,9⋅10−3 g/dm3. The gravimetric and titrimetric methods for the determination of indium using the periodate ion are based on these analytical characteristics [59].
Answering the question whether the ClO4− ion is included in the inner coordination sphere of indium, it can be considered proven that indium acidic complexes are not formed in aqueous solutions, and in this case we are only talking about the possibility of the outer-sphere interaction of ClO4− ions with aquocation. However, in a number of organic systems, apparently, their participation in complex formation is possible, but such states, being weaker than contact interactions, are rather difficult to fix. Perchlorate ion and perchloric acid in indium compounds perform primarily the function of a dehydrating agent; therefore, their presence leads to a change in the characteristics of the interaction of ions with water, which is reflected in the physicochemical properties of indium perchlorates.
Apparently, in relatively dilute solutions, the role of ClO4− is reduced to destructuring water, which contributes to the stabilization of hydration shells around hydrophilic indium cations. In concentrated solutions, ClO4− anions enter into some competition with cations for water, as a result of which, in particular, an increase in the asymmetry of coordination water molecules and its additional polarization is possible. Indium (III) cations attach a larger number of layers of water and, to varying degrees, affect its state, and through it, the action spreads further to the property and the boundary medium. Thus, this causes either the destructuring effect or a change in the state of chemical bonds of ClO4− ions in concentrated solutions.
Thus, the ClO4− ion, being structure-forming and exhibiting a protoacceptor ability, in solutions of group III perchlorates forms exclusively solvate-separated ion pairs due to the high enthalpy of hydration of the corresponding metal cations.
\n',keywords:"perchlorate ion, indium, gallium, complexation, ionic state, NMR, IR, extraction, coordination number",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/73887.pdf",chapterXML:"https://mts.intechopen.com/source/xml/73887.xml",downloadPdfUrl:"/chapter/pdf-download/73887",previewPdfUrl:"/chapter/pdf-preview/73887",totalDownloads:22,totalViews:0,totalCrossrefCites:0,dateSubmitted:"July 22nd 2020",dateReviewed:"September 29th 2020",datePrePublished:"December 7th 2020",datePublished:null,dateFinished:"November 3rd 2020",readingETA:"0",abstract:"The possibility of the formation of India perchlorate and mixed ligand complexes has been studied. It is assumed that during the extraction of indium in aqueous solutions of hydrochloric acid at various concentrations and constant ionic strength maintained by the addition of perchloric acid, indium is present in the organic phase in the form of ionic aggregates HClO4 · HInCl4. To study the hydration of Ions, the method of electrical conductivity was carried out in the “In(ClO4)3 - HClO4 - H2O” system. The structure of aqueous solutions of India perchlorates was determined by IR spectroscopy. The structures of trivalent perchlorate India have been established.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/73887",risUrl:"/chapter/ris/73887",signatures:"Radionov Boris Konstantinovich and Svirsky Ilya Anatolievich",book:{id:"10201",title:"Post-Transition Metals",subtitle:null,fullTitle:"Post-Transition Metals",slug:null,publishedDate:null,bookSignature:"Prof. Mohammed Muzibur Rahman, Dr. Abdullah Mohammed Ahmed Asiri and Prof. Thamer Tabbakh",coverURL:"https://cdn.intechopen.com/books/images_new/10201.jpg",licenceType:"CC BY 3.0",editedByType:null,editors:[{id:"24438",title:"Prof.",name:"Mohammed Muzibur",middleName:null,surname:"Rahman",slug:"mohammed-muzibur-rahman",fullName:"Mohammed Muzibur Rahman"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:null,sections:[{id:"sec_1",title:"1. Ionic state of indium in perchlorate solutions",level:"1"},{id:"sec_2",title:"2. Study of ion hydration by the method of electrical conductivity in the system",level:"1"}],chapterReferences:[{id:"B1",body:'Johansson L. The role of the perchlorate ion as ligand in solution//Coordinat. Chem. Revs. 1974. V.12. № 3. Р.241-261.'},{id:"B2",body:'Rosolovsky V.Ya. Complex perchlorates of polyvalent metals. XI Mendeleev Congress on General and Applied Chemistry. Inorganic chemistry and technology of inorganic substances. The science. M.: 1975.S. 82-83.'},{id:"B3",body:'Cozzi D., Vivarelli S. Beitrag zur Chemie des Indiums. // Z. Elektrochem. 1953. Bd. 57. № 16. S. 408-416.'},{id:"B4",body:'White J.M., Kelly P., Li N.C. Dynonyl naphthaline sulphonic acid and tri-n-octylamine as liquid ion-exchangers for the stydy of Fe(ΙΙΙ) and In(ΙΙΙ) chloride complexes // J. Inorg. Nucl. Chem. 1961. V. 16. № 3-4. P. 337-344.'},{id:"B5",body:'Hester R.E., Plane R.A.a) Solvation of metal ions in aqueous solutions: the metal-oxygen bond // Inorg. Chem. 1964. V. 3. № 5. P. 768-769;b) A Raman spectrophotometric comparison of interionic association in aqueous solutions of metal nitrates, sulfates, and perchlorates // Inorgan.Chem. 1964.V. 3. № 5. P.769-770.'},{id:"B6",body:'Hester R.E., Plane R.A., Walrafen G.E. Raman spectra of aqueous solutions of indium sulfate, nitrate, and perchlorate // J. Chem. Phys. 1963. V. 38. № 1.P. 249-250.'},{id:"B7",body:'Hester R.E., Plane R.A. A Raman spectrophotometric comparison of interionic accociations in aqueous solution of metal nitrates, sulfates, and perchlorates // Inorg. Chem. 1964. V. 3. № 5. P. 769-770.'},{id:"B8",body:'Hester R.E., Grossman W.E.L. Low frequency bands in the Raman spectra of aqueous indium (ΙΙΙ) solutions // Spectrochim. Acta. 1967. V. 23A. № 6.P. 1945-1946.'},{id:"B9",body:'Rudolph W.W., Fischer D., Tomneg M.R., Rye C. C. Indium (III) hydration in aqueous of perchlorate, nitrate and sulfate. Raman and infrared spectroscopic studies and ab-initio molecular orbital calculation of indium (III) – water cluster // Phys.Chem.Chem.Phys. 2004. V. 6. № 22. Р. 5145-5155.'},{id:"B10",body:'L.A. Mund Investigation of aqueous solutions of metal perchlorates of the first and third groups of the periodic system of elements by vibrational spectroscopy / Author\'s abstract. dissertation. for a job. learned. step.kand. chem. sciences. L. 1973.25 C. (Leningrad State University named after A.A. Zhdanov).'},{id:"B11",body:'Tuck D.G. The coordination chemistry of In (ΙΙΙ) isreviewed // Coord. Chem. Rev. 1966. № 1. P. 286-291.'},{id:"B12",body:'Latysheva V.A., Myund L.A., Glebovskiy D.N. Protolithic interaction of water with aquacations of some metals according to infrared spectroscopy // J. physical Chemistry. 1972. T. 46. No. 5.S. 1330-1332.'},{id:"B13",body:'Davidyan A.G. The structure of aqueous solutions of metal perchlorates of I-III groups of the Periodic system D.I. 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Magnetic resonance studies of solution containing 115In // Trans. Farady. Soc. 1966. V. 62. № 6. P. 1378-1387.'},{id:"B18",body:'Buslaev Yu.A., Tarasova V.P., Buslaeva M.N., Petrosyants S.P.Investigation of aqueous solutions of electrolytes by NMR on nuclei of cations // Dokl. Academy of Sciences of the USSR. 1973. T. 209. No. 4. C. 882-884.'},{id:"B19",body:'Šmirous F., Čeleda J., Palek M. Contributions to the chemistry of highly concentrated aqueous electrolyte solutions. XXV. Ionophoretic investigation of the association of Al3+, Sc3+, Ga3+ and In3+ ions in concentrated solutions of NaClO4 and LiCI // Collect. Czech. Chem. Communs. 1971. V. 36. № 12. P. 3891-3899.'},{id:"B20",body:'Sakellaridis P., Coromanzou M. Etude spectrophotométrique des solutions chlorhydriques de l’indium // Bull. Soc. chim. France. 1962. № 4. S. 769-771.'},{id:"B21",body:'Schnoor R. The influence of liquid junction potentials on potentiometric determination of the activity coefficient of In3+ ion in concentrate aqueous perchlorate solutions // Z. Phys. Chem. 1989. Bd. 270. № 6. S. 1169-1176.'},{id:"B22",body:'Fratiello A., Vidulich G.A., Cheng C., Kubo V. A direct hydrogen-1 andphosphorus-31 nuclear magnetic resonance cation solvation study of Al(ClO4)3, Ga(ClO4)3, In(ClO4)3, UO2(ClO4)2 and UO2(NO3)2 in water-acetone-dimethylsulfoxide and water-acetone-hexamethylphosphor-amide mixtures // J.Solut. Chem. 1972. V. 1. № 5. P. 433-444.'},{id:"B23",body:'Fratiello A., Lee R.E., Nishida V.M., Schuster R.E. Proton magnetic resonance coordination number study of Al (ΙΙΙ), Be (ΙΙ), Ga (ΙΙΙ), In (ΙΙΙ) and Mg (ΙΙ) in water and aqueous solvent mixtures // J. Chem. Phys. 1968. V. 48. № 8. P. 3705-3711.'},{id:"B24",body:'Lincoln S.F. Solvent coopdination numbers of metal ions in solution //Coopd. Chem. Rev. 1971. V. 6. № 4. August. P. 309-329.'},{id:"B25",body:'Golub A.M., Samoilenko V.M. Influence of non-aqueous solvents on the formation of indium (III) thiocyanate complexes // Ukr. chem. zhurn. 1963. T. 29. No. 6. C. 590-600.'},{id:"B26",body:'Levin I.S., Rodina T.F., Yukhin Yu.M. et al. Extraction of elements of the subgroup gallium and arsenic from solutions of oxygen-containing acids with di- (2ethylhexyl) phosphoric acid / In collection of articles. "Chemistry of extraction processes". M .: Science. 1972.S. 262-267.'},{id:"B27",body:'Diamond R.M. The solvent extraction behavior of inorganic compounds. IV. Variation of the distribution quotient with chloride, hydrogen ion held constants // J. Phys.Chem. 1957. V. 61. № 11. Р. 1522-1531.'},{id:"B28",body:'Hasegawa Y., Takeuchi H., Sekine T. The behavior of indium(ΙΙΙ) complexes in several liquib-liquib distribution system. 2. The extraction of indium (ΙΙΙ) halide and thiocyanate complexes into 4-methyl-2-pentanone, 4-methyl-2-pentanol, or nitrobenzene // Bull. Chem. Soc. Japan. 1972. V. 45. № 5.Р. 1388-1394.'},{id:"B29",body:'Brunette J.P., Taneri M., Goetz-Grandmont G., Leroy M.J.F.a) Synergic extractions of indium (III) from chloride and perchlorate media 1-phenyl-3-methyl-4-acylpyrazol-5-ones and tri-n-octylphosphophine oxide mixtures in toluene // Solv. Extr. and Ion Exch. 1985. V. 3. № 3. Р. 309-330;b) Extractions of indium (III) from chloride media with 1-phenyl-3-methyl-4-acylpyrazol-5-ones. Synergic effect with high molecular weight ammonium salts // Polyhedron. 1982. V. 1. № 5. Р. 457-460.'},{id:"B30",body:'Genge J.A.R., Salmon J.C. Ion-exchange studies of phosphates. Part ΙΙΙ. Complex formation between tervalent metals and orthophosphoric acid // J.Chem. Soc. 1959. Apr. Р. 1459-1463.'},{id:"B31",body:'Gorokhova L.N., Tsintsevich E.P. Cation exchange of gallium and indium in the presence of perchloric acid and organic solvent // Moscow State University Bulletin. 1966. No. 3. P.113-114.'},{id:"B32",body:'Radionov B.K., Maltsev G.I. Indium in aqueous solutions. Chemistry of rare and trace elements. // Germany, Saarbrücker: LAP LAMBERT Academic Publishig. 2014.-352 p.'},{id:"B33",body:'Golub A.M., Akmyradov R., Uskova S.L.a) Study of indium nitrite complexes in methanol // Izv. Universities. Chemistry and chem. technology. 1974. T. 17. No. 9. S. 1287-1290;b) Coordination compounds of indium nitrite with some organic ligands // J. inorg. chemistry. 1974. T. 19.No. 7.P.1761-1764.'},{id:"B34",body:'Ionov V.I., Chicherina N.Yu. Extraction of indium tenoyltrifluoroacetate from perchlorate and chloride solutions // J. inorg. chemistry. 1979 T. 24. No. 2. S. 465-470.'},{id:"B35",body:'Gusev N.I. Study of ion hydration by the method of electrical conductivity a) ХΙΙΙ. Some issues of ion hydration and the structure of solutions // J. physical chemistry. 1973. T. 47. No. 9. S. 2327-2331;b) ΙΧ. Association in acidic perchlorate solutions // J. physical Chemistry. 1973. T. 47. No. 2. S. 324-328;c) Χ. Change in the number of water molecules oriented by cations in the temperature range from 10 to 50 ° C // Ibid. 1973. T. 47. No. 1. S. 96-100.'},{id:"B36",body:'Pestova O.N., Davidyan A.G., Myund L.A., Khripun M.K. Solubility of perchlorates of aluminum, gallium, indium in water // J. general chemistry. 2011. T. 81.No. 8.S. 1237-1241.'},{id:"B37",body:'Heinje G., Luck W.A.P., Heinzinger K. Molecular dynamics simulation of an aqueous NaClO4 solution // J. Phys. Chem. 1987. V. 91. № 2. Р.331-338.'},{id:"B38",body:'Paskalev N. Basis perchlorates of indium (III) // Dokl. Bolg. AN. 1967. T.20. № 6. C. 549-552.'},{id:"B39",body:'Celeda J., Tuck D.G. A densimetrie study of indium (III) species in meneral acid solutions // J. Inorg. and Nucl. Chem. 1974. V. 36. № 2. P. 373-378.'},{id:"B40",body:'Maeda M., Ohtaki H. An X-ray diffraction study on the structure of the aqua indium (III) ion the perchlorate solution // Bull. Chem. Soc. Jap. 1977. V. 59. № 7. P. 1893-1894.'},{id:"B41",body:'Ilyukhin A.B., Malyarik M.A. The crystal structure of indium perchlorates [In(Н2О)6](ClO4)3 and [In(Н2О)6](ClO4)3⋅3H2O // J. inorg. Chemistry. 1999. T. 44.No 4.S. 532-535.'},{id:"B42",body:'Seward T. M., Henderson C. M., Charnock J. M. Indium (III) chloride comphlexing and solvation in hydrothermal solutions to 350°C: an EXAFS study // Chem. Geol. 2000. V. 167. № 1-2. P. 117-127.'},{id:"B43",body:'Golub A.M., Samoilenko V.M. Potentiometric study of the composition and strength of ion solvates, J. inorg. chemistry ,. 1965. T. 10. No. 2. S. 328-331.'},{id:"B44",body:'Haladjian J., Bianco P. Préparation des perchlorates ďaluminium, de gallium et ďindium anhydres en solution méthanolique // Chemia. 1973. V. 27. № 11. Р. 588-589'},{id:"B45",body:'Petrů F., Kůtek F.Ü ber die thermische Zersetzung von Perchlorates einiger Metalle der III. Gruppe // Z. Chem. 1964. Hf. 1. Jg 4. S. 33-34.'},{id:"B46",body:'Carty A.J., Tuck D.G. Co-ordination compounds of indium. Part.I. Some cationic complexes of indium (III) // J. Chem. Soc. 1964. Suppl. № 2. Р. 6012-6017.'},{id:"B47",body:'Ishihara K., Funahashi S., Tanaka M. Mechanistic study on the complex formation of aluminum (III), gallium (III), and indium (III) ions in dimethyl sulfoxide and N,N-dimethylformamide // Inorgan. Chem. 1986. V. 25. № 16. P. 2898-2901.'},{id:"B48",body:'Cherkasova T.G., Tatarinova E.S. Crystal structure of indium hexa (dimethyl sulfoxide) perchlorate (ΙΙΙ) // Izv. VUZov. Chemistry and chemical technology // 1997. V. 40. No. 2. P. 26-28.'},{id:"B49",body:'Babakulov N., Latysheva V.A.a) Bulk properties of aqueous solutions of aluminum, gallium and indium perchlorates // Izv. Universities. Chemistry and chemical technology. 1973. T. 16. No. 9. S. 1449-1451;b) Heat capacity of aqueous solutions of metal perchlorates of the third group of the periodic system // J. physical chemistry. 1974. Vol. 48. No. 4. P.1012-1014.'},{id:"B50",body:'Babakulov N., Grigorieva E.G., Latysheva V.A. The speed of sound and the compressibility of aqueous solutions of perchlorates of some metals of the second and third groups of the Periodic Table D.I. Mendeleev. // Rukop. dep. VINITI. 1976. No. 3004-76 Dep.'},{id:"B51",body:'Babakulov N., Latysheva V.A., Shchukarev S.A. The nature of p- and d-metal cations of the third group of the periodic system and the properties of aqueous solutions of their perchlorates // J. general chemistry. 1977. Vol. 47, No. 1.S. 23-31.'},{id:"B52",body:'Penkina N.V., Smaev V.N. Viscosity and density of aqueous solutions of perchlorate cations of group ΙΙΙ. ΙΙ. Gallium and indium perchlorates. // Rukop. dep. VINITI. 10/04/74. No. 2597-74 Dep.'},{id:"B53",body:'Latysheva V.A. Water-salt solutions. Systems approach. SPb .: Publishing house. St. Petersburg. un-that. 1998.344 S.'},{id:"B54",body:'Latysheva V.A. Heat capacity of solutions and symmetry of aqua ions // Journal of Physics. chemistry. 1974. T. 48. No. 5. S. 1315. Rukop. dep. VINITI. 04.02.74. No. 213-74 Dep.'},{id:"B55",body:'Latysheva V.A., Myund L.A., Glebovskiy N.D. The state of aqua ions in aqueous solutions of metal perchlorates of 1-3 groups of the periodic system of metals according to vibrational spectroscopy / In collection. "Problems of modern chemistry of coordination compounds" L .: LGU, 1975. Issue 5.S. 85-121.'},{id:"B56",body:'Rogers T.E., Waind G.M. Spectrophotometric studies of concentrated perchlorate solutions. Part. I. Thallic perchlorat // Trans. Far. Soc. 1961. V. № 8. P. 1360-1370.'},{id:"B57",body:'Mathers F.C., Schluederberg C.G. Obtaining perchlorate, iodate, selenate and cesium-selenium indium alum // J. Amer. Chem. Soc. 1908. V. 30. P. 211-215.'},{id:"B58",body:'Ivanov-Emin B.N., Rybina V.I., Zaitsev B.E. et al.a) Study of aluminum iodates and elements of the gallium subgroup // Coord. chemistry. 1979. T. 5. No. 4. S. 514-519;b) Investigation of the thermal stability of aluminum iodates and elements of the gallium subgroup // J. inorg. chemistry. 1981. T. 26. No. 12. S. 3227-3230.'},{id:"B59",body:'Vertizade A.A., Mekhtiev M.M. Gravimetric and titrimetric methods for the determination of indium using the periodate ion // Zh. analyte. chemistry. 1970. T. 25. No. 6. S. 1097-1101.'}],footnotes:[],contributors:[{corresp:null,contributorFullName:"Radionov Boris Konstantinovich",address:null,affiliation:'
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