Characterization of membranes in non-steady state

FINAL DEGREE PROJECT Degree of Chemical Engineering CHARACTERIZATION OF MEMBRANES IN NON-STEADY STATE Report and Annexes Author: ROGOVYK, VITALIY Director: CORTINA PALLAS, JOSE LUIS Co-Director: YAROSHCHUK, ANDRIY Summon: May 2019 CHARACTERIZATION OF MEMBRANES IN NON-STEADY i I. Abstract Ion exchange membranes (IEMs) have been established as a key component in industrial water desalination and electrolysis processes. Thus, nowadays, they are being studied and developed for application in new energy conversion and storage systems as well as efficient desalination and wastewater treatment processes. Ion permselectivity between counter- and co-ions, the most essential property in IEMs, makes these processes possible and/or efficient. Additionally, ion selectivity between different counter-ions is required for these novel processes to be efficient. However, they show minimal selectivity among monovalent ions, which limits their use in ion separations. Recent studies show that modification of ion exchange membranes with polyelectrolyte multilayers leads to exceptional monovalent/divalent ion selectivities. To better understand the mechanisms of transport of ions through active layers of membrane (polyelectrolyte multilayers) and to be able to perform its predictive modelling one needs to know electrochemical properties of membrane active layers. Their determination is strongly influenced by the multilayer structure of membranes. Conventional linear steady-state techniques yield information on the membrane average properties (involving both active layer and support) alone. In this study, ion-exchange membranes were modified with polyelectrolyte solutions and the prepared membranes were evaluated and characterized using different experimental techniques. The concentration-step technique was used to study the electrochemical properties of active layers of a commercial polymer FujiFilm Type 1 CEM and Type 1 AEM. An experimental set-up was built and the theory of non-steady-state membrane potential was used to analyse the information collected from various modes of experimental measurements. Report ii II. Acknowledgments I would like to thank my supervisor for giving me the opportunity to pursue my enthusiasm for both physics and chemistry, and for allowing me to play in the lab to my heart’s content. His enthusiasm and positive attitude often helped me through rough patches. Also, I would like to give my gratitude to my friend Sergio. He helped me a lot with a pair of electrodes. If not his knowledge of electronic engineering, my study would be far away from finishing now. . CHARACTERIZATION OF MEMBRANES IN NON-STEADY iii III. Index I. ABSTRACT _______________________________________________________ I II. ACKNOWLEDGMENTS ____________________________________________ II III. INDEX _________________________________________________________ III 1. INTRODUCTION _________________________________________________ 5 1.1. Polyelectrolyte multilayers (PEMs) .......................................................................... 8 1.2. Objectives ............................................................................................................... 10 2. THEORY _______________________________________________________ 11 2.1. Equations in a non-stationary state ....................................................................... 11 2.2. Operation of the instruments ................................................................................ 15 2.2.1. FT-IR (Fourier Transform Infra-Red) Spectroscopy .............................................. 15 2.2.2. Field Emission Scanning Electron Microscope (FESEM)....................................... 17 2.2.3. Energy-dispersive X-ray spectroscopy ................................................................. 18 3. EXPERIMENTAL METHOD ________________________________________ 20 3.1. Preparation of solutions. ....................................................................................... 20 3.2. Modification of membranes. ................................................................................. 22 3.3. Data acquisition. .................................................................................................... 23 4. RESULTS AND DISCUSSION _______________________________________ 26 4.1. Electrical response of active layers in the non-steady state. ................................ 26 4.2. FESEM Surface images. .......................................................................................... 30 4.2.1. Comparison between uncoated membrane (Fujifilm Type1 AEM) and modified membrane (5 bilayers (PSS/PAH)) ........................................................................ 30 4.2.2. Comparison between uncoated membrane (Fujifilm Type1 CEM) and modified membrane (5 bilayers (PAH/PSS)) ........................................................................ 32 4.3. Energy-dispersive X-ray spectroscopy ................................................................... 33 4.3.1. Bare Fujifilm Type1 AEM and modified membrane (5 bilayers (PSS/PAH)). ....... 33 4.3.2. Bare Fujifilm Type1 CEM and modified membrane (5 bilayers (PAH/PSS)). ....... 35 4.4. FT-IR ATR ................................................................................................................ 36 5. ENVIRONMENTAL IMPACT AND SAFETY _____________________________ 38 CONCLUSIONS ______________________________________________________ 39 ECONOMIC ANALYSIS ________________________________________________ 40 Report iv BIBLIOGRAPHY _____________________________________________________ 41 ANNEX I. CATION EXCHANGE MEMBRANE IN SOLUTION OF KCL ______________ 45 ANNEX II. ANION EXCHANGE MEMBRANE IN SOLUTION OF KCL ______________ 53 ANNEX III. CATION EXCHANGE MEMBRANE IN SOLUTION OF LICL ____________ 61 ANNEX IV. ANION EXCHANGE MEMBRANE IN SOLUTION OF LICL _____________ 69 ANNEX V. ALGORITHM. ______________________________________________ 77 ANNEX VI. SAFETY DATA SHEET. _______________________________________ 80 CHARACTERIZATION OF MEMBRANES IN NON-STEADY 5 1. Introduction Water is one of the most precious and important resources in industrial production. Nevertheless, the discharge of untreated industrial wastewater is one of the most general performances threatening to the surroundings. The wastewater treatment has become a significant issue. Recently, ion exchange membranes (IEMs) have significantly contributed to overcoming these problems associated with energy, environment and water treatment. Thus, there is an increasing worldwide interest in the use of IEMs to develop renewable energy sources. IEMs are an important class of dense polymeric membranes that bear fixed charges in the polymer matrix. Ion exchange membranes are typically composed of hydrophobic substrates, immobilized ionfunctionalized groups, and movable counter-ions. Depending on the type of ionic groups, IEMs are broadly classified into cation exchange membranes (CEMs) \ and anion exchange membranes (AEMs). Naturally, the ion-functionalized groups attached to the IEMs will dissociate after the penetration of sufficient water molecules, releasing cations or anions for the transfer of corresponding ions. The most common functional moieties in CEMs contain sulfonic acid, phosphoric acid and carboxylic acid groups (–SO3-,–PO32 and –COO-). Quaternary ammonium cations (NR4+), imidazole cations (C3H5N2+), and guanidinium cations (CH6N3+) are generally anchored onto the polymer matrix to obtain AEMs. Because the ionic groups absorb water, membranes must contain a high degree of crosslinking or insoluble phases to limit swelling. These membranes can selectively allow the passage of oppositely charged ions (counter-ions) while obstructing similarly charged ions (co-ions) like shown in figure 1. However, most ion-exchange membranes exhibit modest selectivities among various cations or anions, which limits their application in salt separations such as water softening, NaCl purification, and isolation of Li+ from other alkali metals. IEM permselectivity for counter-ions was first elucidated by Donnan, thus, the mechanism is referred to as the Donnan effect or Donnan exclusion (towards co-ions). Due to this ion permselectivity, several industrial processes based on IEMs, including electrodialysis (ED), diffusion dialysis (DD), and electrolysis, have been established. Report 6 Figure 1: Scheme of K+/Na+ exchange in DD through a cation exchange membrane In the electrodialysis (ED) process, ions from the diluted compartment flow-through ion exchange membranes (IEMs) to concentrated compartment under the electric field. The key element of the electrodialysis process is the IEM, because of the selectivity function of ions. Many system designs and material modifications have been introduced in order to apply this process in various industries including the chemical, food, pharmaceutical, semiconductor and wastewater industry. IEMs have the effect for the separation of positive or negative ions, it is usually used to produce drinking water from seawater and brackish water simultaneous production of salt from seawater concentration. It is also a low cost and effective method for the treatment of salinity waters and economical in the high concentration of ions. In potential applications, DD using a thin flow cell with an acid receiving phase could extract contaminating ions away from Li+ if the cation-exchange membrane were highly permeable and selective for the contaminating ions. However, low selectivity limits DD applications, most of which focus on separating ions with different valences. Apart from ED and DD, IEMs have also been widely studied as a key component in flow batteries as well as some emerging new applications including membrane capacitive deionization (MCDI), reverse electrodialysis (RED), microbial fuel cells (MFCs), and ion exchange membrane bioreactors (IEMBs). IEMs with low fixed charge density are also studied as chlorine-tolerant membranes in reverse osmosis (RO) for seawater desalination. As summarized in Table 1, these different processes employ different driving forces and aim to help address the increasing global concern on energy shortage, environmental issues, and depletion of drinking water sources. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 7 With the growing number of IEM applications, permselectivity between counter- and co-ions as well as counter-ions of different (monovalent and multivalent, e.g. Li+ and Mg2+) or equal (e.g. NO3- and Cl-) valences, is desirable. Thus, processes such as flow batteries, diffusion dialysis (DD), microbial fuel cells (MFCs), and ion exchange membrane bioreactors (IEMBs) all require high membrane permselectivity between counter-ions of different valences. In flow batteries, the essential function of an IEM is to isolate the ions of redox couples that are involved in electrode reactions to prevent self-discharge, while allowing the transfer of specific ions (charge carriers) across the membrane at a high rate to complete the electric circuit. Membrane-based separation of Li+ from other metal ions is also significant because of the importance of Li-containing refrigerants and batteries. Methods for isolating Li+ include solvent extraction, nanofiltration, low-pressure reverse osmosis, and ED. Selective ion exchange membranes may provide a platform that can efficiently isolate Li+ from other monovalent cations. For the application of IEMs in IEMBs and MFCs, high permselectivity between the counter-ions is crucial for system efficiency. In the case of IEMBs, the selective transport of toxic oxyanions (ClO4-, NO3-, BrO3- ) over other multivalent anions (SO42-, HPO42-) under Donnan dialysis conditions is desirable to efficiently treat drinking water polluted with these monovalent anions. Recent studies employing commercial monovalent anion selective membrane have exhibited the best performance in terms of selective removal of monovalent anions to the recommended safety levels. However, the high price of monovalent anion selective membranes is a hurdle for the application of this technology. In microbial electrochemical systems such as MFC, selective H+ transport in the presence of Na+ with a substantially higher concentration is an even greater challenge. The monovalent selectivity of IEMs is the special function for those applications in which the monovalent ions separate from mixtures containing multivalent ions. In this regard, many important investigations about the monovalent ions selectivity technology are developing and large scale applications of this type of membranes have been already accomplished for the purpose of the monovalent selective in industrial. Recently, several papers reported remarkable selectivities between Table 1: Different processes that employ ion exchange membranes (IEMs). Report 14 where we have scaled the transmembrane co-ordinate on the active layer thickness, ξ≡ꭓ/la, and time on the diffusion relaxation time of active layer defined in this way: Index a denotes the properties of active layer. Coefficients βi are defined in this way: By definition βi≡1. We have introduced also this notation: By using equation 12 to make a graphic, one can make predictive modelling of ion-transport mechanisms through the active layer, in this case, polyelectrolyte multilayer. Depending on the characteristic time, the curves will shift more to the right or left as shown in figure 3. Two different ions, the characteristic time of which is different, will make one more permeable to others. This is one of the goals of this project to see if the characteristic time of Li+, K+ and Clis differing. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 15 Figure 3: Concentration-step method: chemical potential difference across active layer against dimensionless time: r1=rp=10 (solid); =33 (dashed), =100 (dotted). Time scaled with Eq. (12). 2.2. Operation of the instruments 2.2.1. FT-IR (Fourier Transform Infra-Red) Spectroscopy When it is said that a bond between two atoms has a certain length, an average length is established because a bond behaves as if it were a spring in vibration that connects two atoms. These characteristic vibrations are called natural frequency of vibration. Each vibration of tension and flexion of a bond in a molecule occurs with a characteristic frequency. Infrared radiation has just the right energy that corresponds to the energy of the tension and bending vibrations of organic molecules. Some of this energy represented in wavelength is shown in table 2. Report 16 Table 2: Fourier transform infrared spectroscopy peaks and functional groups. When a compound is bombarded with radiation of a frequency that exactly matches the frequency of one of its vibrations, the molecule absorbs energy. By experimentally determining the wave number of the energy absorbed by a particular compound, one can find out what types of bonds it has. IR Spectroscopy is used for qualitative identification of organic and inorganic compounds. In infrared spectrum can be divided into two areas. The region of 4000 cm-1 to 1400 cm-1 is where most of the functional groups show absorption bands. This is called the region of the functional groups. The region of 1400 cm-1 to 600 cm-1 of the spectrum is called fingerprint region because it is characteristic of the compound as a whole, just as a fingerprint is characteristic of an individual. One of the available methods of sampling is attenuated total reflectance (ATR). ATR is a sampling technique used in conjunction with infrared spectroscopy which enables samples to be examined directly in the solid or liquid state without further preparation. ATR uses a property of total internal reflection resulting in an evanescent wave. Principle of operation of the ATR accessory is shown in figure 4. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 17 Figure 4: Schematics of ATR device. A beam of infrared light is passed through the ATR crystal in such a way that it reflects at least once off the internal surface in contact with the sample as shown in figure 4. This reflection forms the evanescent wave, which extends into the sample. The energy of evanescent wave is absorbed by the sample and reflected radiation is returned to the detector. 2.2.2. Field Emission Scanning Electron Microscope (FESEM) A FESEM is a microscope that works with electrons instead of light. These electrons are liberated by a field emission source. The object is scanned by electrons according to a zig-zag pattern. Electrons are liberated from a field emission source and accelerated in a high electrical field gradient. Within the high vacuum column, these so-called primary electrons are focussed and deflected by electronic lenses to produce a narrow scan beam that bombards the object. As a result, secondary electrons are emitted from each spot on the object. The angle and velocity of these secondary electrons relate to the surface structure of the object. A detector catches the secondary electrons and produces an electronic signal. This signal is amplified and transformed into a video scan-image that can be seen on a monitor or to a digital image that can be saved and processed further. In order to observe a sample with an SEM, objects are first made conductive for current. This is done by coating them with an extremely thin layer (1.5 - 3.0 nm) of gold or gold-palladium. Further, objects must be able to sustain the high vacuum and should not alter the vacuum, for example by losing water molecules or gasses. Metals, polymers and crystals are usually little problematic and keep their structure in the SEM. Biological material, however, requires a prefixation, e.g. with liquid nitrogen (cryo-fixation) or with chemical compounds. Simplified schematics of operation of the FESEM equipment is shown in figure 5. Report 18 Figure 5: Schematics of scanning electron microscope 2.2.3. Energy-dispersive X-ray spectroscopy Energy Dispersive X-Ray Spectroscopy (EDS or EDX) is a chemical microanalysis technique used in conjunction with scanning electron microscopy (SEM). The EDS technique detects x-rays emitted from the sample during bombardment by an electron beam to characterize the elemental composition of the analyzed volume. Features or phases as small as 1 µm or less can be analyzed. When the sample is bombarded by the SEM's electron beam, electrons are ejected from the atoms comprising the sample's surface. The resulting electron vacancies are filled by electrons from a higher state, and an x-ray is emitted to balance the energy difference between the two electrons' states. The x-ray energy is characteristic of the element from which it was emitted. The EDS x-ray detector measures the relative abundance of emitted x-rays versus their energy. The detector is typically lithium-drifted silicon, solid-state device. When an incident x-ray strikes the detector, it creates a charge pulse that is proportional to the energy of the x-ray. The charge pulse is converted to a voltage pulse (which remains proportional to the x-ray energy) by a charge-sensitive preamplifier. The signal is then sent to a multichannel analyzer where the pulses are sorted by voltage. The energy, as determined from the voltage measurement, for each incident x-ray is sent to a computer for display and further data evaluation. The spectrum of x-ray energy versus counts is evaluated to determine the elemental composition of the sampled volume. The simplified principle of the detection of the X-ray is shown in figure 6. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 19 Figure 6: Schematics of a generation of X rays. Report 20 3. Experimental method 3.1. Preparation of solutions. To begin with, it was necessary to prepare solutions of salts of various concentrations. The working solutions were chosen potassium chloride and lithium chloride with a concentration of 0.01 M and 0.1M. Below is described the process preparation of working solutions. Figure 7: a) Weigh of beaker. b) Beaker with salt. Firstly, the beaker was weighed, and then the required amount of the salt was weighed down. Then the solute was mixed with distilled water and poured into a 1000 ml volumetric flask. By the same beaker it was poured a little more distilled water to dissolve remaining solute that could remain in the walls of the glass, then this water was also added to the volumetric flask. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 21 Figure 8: a) Empty flask. b) Filled flask. Eventually, to the volumetric flask was added the required amount of distilled water to reach the mark as shown in figure 8. The same process of preparation of solutions described previously was used to prepare a solution of polyelectrolytes. The difference was that the 50 ml volumetric flask was used instead. Figure 9: Flask with PSS. Since PAH is a weak polyelectrolyte, its pH should be lowered to 2.4, it would help to dissociate polyelectrolyte, and its fixed groups (cationic groups) will be able to interact with anionic groups. Report 22 Figure 10: pH-meter. Figure 10 shows us that the pH level of the solution of poly(allylamine hydrochloride) was lowered till 2.4. 3.2. Modification of membranes. The modification of the membranes consisted of depositing thin layers of polyelectrolytes on the surface of the membrane. If the membrane to be modified is an anionic membrane, which mostly contains fixed cationic groups, then the first layer of the polyelectrolyte to be deposited on it, is polyanion (PSS). And if it is a cationic membrane, the first layer should be of polycation (PAH). The important thing to remember is that the membrane must be equilibrated with the working solution of lower concentration (0.01 KCl or LiCl). To make this happen, it is necessary to leave the membranes one day (24 h) in 0.01 M of salt solution. Below is the described process of modification of membranes. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 23 Figure 11: Fixing capsule. The first step to modify membrane is to fasten it to the capsule. When the membrane is securely fixed as shown in figure 11, one should proceed to apply layers of polyelectrolytes on it. Figure 12: Modification of membrane applying polyelectrolytes. Between every coating should pass approximately five minutes and after that time, the membrane must be washed with distilled water. The remaining water on the top of the membrane should be removed with the Pasteur pipette. 3.3. Data acquisition. Before measure membrane potential, the auxiliary test cell was used to determine the potential of asymmetry of two Ag/AgCl reference electrodes. The asymmetry potential between the measuring electrode was measured separately and subtracted from the measured membrane-potential transients. Report 30 Figure 21: Electrical response in active layer in AEM 4.2. FESEM Surface images. 4.2.1. Comparison between uncoated membrane (Fujifilm Type1 AEM) and modified membrane (5 bilayers (PSS/PAH)) The effect of the alternate deposition of PSS and PAH assemblies on the surface of the modified membranes was further observed by FESEM. Figure 22(a) and figure 23(a) shows the FESEM images of unmodified AEM and figure 22(b) and figure 23(b) shows the FESEM images of modified AEM and the PSS/PAH alternative deposition multilayer on the membrane surface. In the micrograph of figure 24, the deposition multilayer on the membrane surface can be clearly distinguished from the membrane substrate. The interspaces cannot be distinguished between PSS layers and PAH layers and the thickness of the modified membrane was about 2.0 - 2.3 micrometres with 5 bilayers. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 31 Figure 22: Comparison between a) bare AEM and b) coated AEM. 100 μm Figure 23: Comparison between a) bare AEM and b) coated AEM. 10 μm Figure 24: PEMs on AEM In the study “An anion exchange membrane modified by alternate electro-deposition layers with enhanced monovalent selectivity” studied by Zhao et al. [6] it is also concluded that the thickness of PEM it’s around 3.6-3.8 μm. Report 32 Figure 25: Cross sectional SEM micrographs of (A) unmodified membrane and (B) membrane modified with 9 bilayers of PSS/HACC electro-deposition multilayer on the membrane surface. Y. Zhao et al. [6] However, Bruening et al. in their work “Layered Polyelectrolyte Films as Selective, Ultrathin Barriers for Anion Transport” demonstrated that 5 bilayers of PAH/PSS have less than 25 nm of thickness [7]. 4.2.2. Comparison between uncoated membrane (Fujifilm Type1 CEM) and modified membrane (5 bilayers (PAH/PSS)) In the images below, one could say that there is a slight difference between the uncoated membrane figures 26(a) and 27(a) and the modified membrane figures 26(b) and 27(b). Nevertheless, one couldn't affirm that there is any thin film of polyelectrolyte like it was seen in modified anion exchange membranes. Figure 26: Comparison between a) bare CEM and b) coated CEM. 100 μm CHARACTERIZATION OF MEMBRANES IN NON-STEADY 33 Figure 27: Comparison between a) bare CEM and b) coated CEM. 1 μm 4.3. Energy-dispersive X-ray spectroscopy 4.3.1. Bare Fujifilm Type1 AEM and modified membrane (5 bilayers (PSS/PAH)). Figure 28 shows us the spectre of the bare membrane, it's spectre we need to compare with the spectrum of the modified membrane. The x-axis corresponds to the energy that bears the primary electrons (in kilo electron volts) and the y-axis corresponds to the intensity of radiation or the frequency of the strike of primary electrons into a certain atom. Figure 28: EDS spectrum for a a) general view of an uncoated membrane and b) specifically of one of the visible “fibers”. In figure 29(a) we can observe almost identical spectrum as in figure 28(a), however, we can see that there are other peaks that correspond to sulfur. And if we search the zone where membrane looks well Report 34 coated then these peaks become more distinguished. In concret, the biggest peak in figure 29(b) probably come from PAH that contains the chlorine. Figure 29: EDS spectrum of a modified membrane: a) general view b) zoom to a zone where the membrane looks wellcoated by the polyelectrolyte. One can also estimate the peak in Figure 30(b) that corresponds to the sulfur contained in the PSS in sulfonate form. One can speculate why two chlorine and sulfur peaks do not appear of the same size in one image. This could be possible because the intensity of excitement of one atom is major than in other. The layer of one polyelectrolyte hides beneath the layer of the other polyelectrolyte and is why the intensity of second is lower. Still, is also true that the radiation could come from different clots which hadn't been washed out from the membrane surface with water. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 35 Figure 30: Comparison between a) genral zone and b) región well-covered by the polyelectrolyte. 4.3.2. Bare Fujifilm Type1 CEM and modified membrane (5 bilayers (PAH/PSS)). The spectrum of bare membrane corresponds to figure 31 (a). In figure 31 (b), a large sulfur peak can be recognized, and a sodium peak can also be seen to the right of it, which means that the poly(sodium 4-styrenesulfonate) is present on the surface of the membrane. Nevertheless, in the case of PAH, it was difficult to find a zone where its radiation would be visible. But if we assume that the membrane is well washed with distilled water, and remember that the cationic membrane is mainly in its structure has negative immobilized groups, it would be very difficult to PSS stick to the surface of the membrane. The most reasonable is that under the PSS layer there is a layer of positively charged PAH. Report 36 Figure 31: EDS spectrum for a general view of a) uncoated membrane and for b) zone of a modified membrane where the membrane looks well-coated by the polyelectrolyte. 4.4. FT-IR ATR Figure 32: Infrared spectrometry CHARACTERIZATION OF MEMBRANES IN NON-STEADY 37 Seeing the infrared spectrometry in figure 31, it can be said that there is no appreciable difference between membrane without electrolytes and with the membrane. The problem lies in the fact that there is no work to compare, only with the study published by Zhao et al. and besides it is very different from our spectrum. Figure 33: Infrared spectrometry. Y. Zhao et al. [9]. Report 38 5. Environmental impact and safety This work doesn't present many chemical experiments and as a consequence, there are not many chemical reagents that can make a serious impact on the environment. However, the usage of ion exchange membranes can have a significant impact on the environment if we don`t take care of end- of-life membranes. There are many options as this membranes can be useful in the future. Reuse is the option where the membrane elements in whole or in part and with little or no conversion could be used in another lower specification application. Recycling is other option, which involves physically transforming the membrane or its components so that they can be regenerated into other useful products. Energy recovery option mainly concerns the combustion of the polymer components of the membranes by oxidation of the organic material to produce energy. Unfortunately, disposal to landfill is currently the only available option for end-of-life membranes. Another perilous component used in this project is HCl that can make a great impact on the environment and should be recycled. Acidification of inland waters has very serious effects on aquatic ecosystems. It has been shown that most of the organisms that make up freshwater ecosystems are sensitive to acidification, producing alterations at all trophic levels. Also, important effect of the acidification of rivers and lakes is the increase in the content of metal ions, such as aluminium ion, dissolved in water. The decrease of the pH level in the water varies the chemical composition of these since ions of heavy metals are liberated to the water that at higher pH were immobilized in insoluble forms. Polyelectrolytes, on the other hand, do not present a danger to the environment and are used in water treatment, but according to Paxéus [29] that levels of PEs will increase with time in soils continuously amended with sludge. This must be considered negative since PEs may exert long-term harmful effects that we can not predict today. Safety information and other information about chemical reagents can be found in the annexes. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 39 Conclusions In this work we have used layer by layer method to deposit the electrolytes on the surface of the cationic and anionic membranes. Then we applied the concentration step technique to measure the electrical response of polyelectrolytes multilayers and see the impact of the active layer on the transport of the ions. The graphs of modified membranes and bare membranes (in the annexes) show us that there is a difference between a modified membrane and bare membrane. This means two things: the first one is that there are PEM on the surface of the membrane, and the second one is that with polyelectrolyte multilayers is possible to control permselectivity of the membrane. If we look at figure 20 we can see what the characteristic time of ion lithium is a bit longer than potassium, this means that lithium takes longer and with more difficulties to pass the polyelectrolyte layers. If we achieve improving these characteristics (relaxation time) we could make the membrane permeable for potassium ions and almost impermeable to lithium ions. The second part of the work consisted of verifying and checking if there are PEMs onto the surface of the membranes. To accomplish this, three techniques were used. The first is infrared absorption spectroscopy, which did not give clear results, since no appreciable difference could be observed between the modified membrane and the bare membrane, and there are not many works that can be compared. In the second technique, we used FESEM to see the polyelectrolyte on the surface of the membrane. But the results were contradictory with some previous studies performed in this field. Thus in the Bruening et al. (Bruening, 2000) study, they confirm that the thickness of PEMs is less than a couple of tens of nanometers while in other study performed by Zhao et al. (Zhao, 2018) confirms and demonstrates with an image also taken by FESEM that thickness is in the order of micrometres. According to the photos obtained in anionic membranes, we can also say that the thickness is more or less 2 micrometres, however, it is also possible that this is a polyelectrolyte clot that got stuck. In the cationic membranes, on the other hand, can't be seen thicknesses as big as in anionic which can support the study of Bruening et al. (Bruening, 2000). And the last method used to see if polyelectrolytes are indeed onto the membranes was energy-dispersive X-ray spectroscopy that seemingly confirms that there were polyelectrolytes in the membranes because if we look at the background of spectroscopy of bare membrane alone and at the modified membrane, it shows that there is a difference. Annexes 46 Figure 35: All experiments with bare membrane. Solution KCl. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 47 Figure 36: All experiments with bare membrane. Solution KCl. Annexes 48 Figure 37: Average transmembrane potential of the bare CEM with error bars. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 49 Figure 38: All experiments with coated membrane. Solution KCl. Annexes 50 Figure 39: Average transmembrane potential of coated CEM with error bars. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 51 Figure 40: Comparison. Annexes 52 Figure 41: Comparison with absolute error CHARACTERIZATION OF MEMBRANES IN NON-STEADY 53 Annex II. Anion exchange membrane in solution of KCl Figure 42: All experiments with bare membrane. Solution KCl. Annexes 54 Figure 43: All experiments with bare membrane. Solution KCl. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 55 Figure 44: Average transmembrane potential of the bare AEM with error bars. Annexes 62 Figure 51: All experiments with bare membrane. Solution LiCl. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 63 Figure 52: Average transmembrane potential of the bare CEM with error bars. Annexes 64 Figure 53: All experiments with coated membrane. Solution LiCl. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 65 Figure 54: All experiments with coated membrane. Solution LiCl. Annexes 66 Figure 55: Average transmembrane potential of coated CEM with error bars. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 67 Figure 56: Comparison. Annexes 68 Figure 57: Comparison with absolute error CHARACTERIZATION OF MEMBRANES IN NON-STEADY 69 Annex IV. Anion exchange membrane in solution of LiCl Figure 58: All experiments with bare membrane. Solution LiCl. Annexes 70 Figure 59: All experiments with bare membrane. Solution LiCl. CHARACTERIZATION OF MEMBRANES IN NON-STEADY 71 Figure 60: Average transmembrane potential of the bare AEM with error bars. Annexes 78 xlabel('Time (s)'); ylabel ('Potential (mV)'); legend (exp{i}); xlim([0.3 10]); legend({exp{i}},'FontSize',18); end figure x=4; exp=cell(1,x); for i=1:x exp{i}=['1exp' num2str(i)]; semilogx(t{i},p{i}); grid on; xlabel('Time (s)'); ylabel ('Potential (mV)'); legend (exp{i}); xlim([0.3 10]); legend({exp{i}},'FontSize',18); hold on; end Annexes 80 Annex VI. Safety data sheet. Product name : Potassium Chloride, Reagent Manufacturer/Supplier Trade name : Manufacturer/Supplier Article number : S25484 Recommended uses of the product and uses restrictions on use : Manufacturer Details : AquaPhoenix Scientific 9 Barnhart Drive, Hanover, PA 17331 Supplier Details : Fisher Science Education 15 Jet View Drive, Rochester, NY 14624 Emergency telephone number : Fisher Science Education Emergency Telephone No.: 800-535-5053 Classification of the substance or mixture : Irr i tant Skin irritation, category 2 Eye irritation, category 2A AcTox Oral 5 skin corr./irrit. 3 Serious EyeDam/Irri. 2 Terrestrial Vertebrate ExoTox 2 Hazards Not Otherwise Classified - Combustible Dust Signal word :Warning Hazard statements : May be harmful if swallowed Causes serious eye irritation Causes skin irritation Toxic to terrestrial vertebrates Precautionary statements : If medical advice is needed, have product container or label at hand Keep out of reach of children Read label before use Wear protective gloves/protective clothing/eye protection/face protection Wash … thoroughly after handling Do not eat, drink or smoke when using this product IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses if present and easy to do. Continue rinsing If eye irritation persists get medical advice/attention If SECTION 1: Identification of the substance/mixture and of the supplier SECTION 2: Hazards identification skin irritation occurs: Get medical advice/attention Call a POISON CENTER or doctor/physician if you feel unwell Combustible Dust Hazard: May form combustible dust concentrations in air (during processing). Other Non-GHS Classification : WHMIS NFPA/HMIS NFPA SCALE (0-4) HMIS RATINGS (0-4) Ingredients: CAS 7447-40-7 Potassium chloride 100 % Percentages are by weight SECTION 4: First aid measures Description of first aid measures After inhalation: Move exposed individual to fresh air. Loosen clothing as necessary and position individual in a comfortable position. Seek medical advice if discomfort or irritation persists. If breathing difficult, give oxygen. After skin contact: Wash affected area with soap and water. Rinse/flush exposed skin gently using water for 15- 20 minutes. Seek medical advice if discomfort or irritation persists. After eye contact: Protect unexposed eye. Rinse/flush exposed eye(s) gently using water for 15-20 minutes. Remove contact lens(es) if able to do so during rinsing. Seek medical attention if irritation persists or if concerned. After swallowing: Rinse mouth thoroughly. Do not induce vomiting. Have exposed individual drink sips of water. Seek medical attention if irritation, discomfort or vomiting persists. Most important symptoms and effects, both acute and delayed: Nausea,Headache, Shortness of breath.Diarrhea. Vomiting. Dehydration. Irritationall routes of exposure.; Indication of any immediate medical attention and special treatment needed: If seeking medical attention, provide SDS document to physician. SECTION 5: Firefighting measures Extinguishing media Suitable extinguishing agents: If in laboratory setting, follow laboratory fire suppression procedures. Use appropriate fire suppression agents for adjacent combustible materials or sources of ignition. Use water spray, dry chemical, alcohol-resistant foam, or carbon dioxide For safety reasons unsuitable extinguishing agents: Special hazards arising from the substance or mixture: SECTION 3: Composition/information on ingredients Annexes 82 Avoid generating dust; fine dust dispersed in air in sufficient concentrations, and in the presence of an ignition source is a potential dust explosion hazard.Keep product and empty containers away from heat and sources of ignition.Thermal decomposition can lead to release of irritating fine dusts, gases or vapors.Not considered to be a fire or explosion hazard under ordinary circumstances. Advice for firefighters: Protective equipment: Use NIOSH-approved respiratory protection/breathing apparatus. Additional information (precautions): Move product containers away from fire or keep cool with water spray as a protective measure, where feasible.Use spark-proof tools and explosion-proof equipment. SECTION 6: Accidental release measures Personal precautions, protective equipment and emergency procedures: Wear protective equipment. Transfer to a disposal or recovery container.Use spark-proof tools and explosionproof equipment.Use respiratory protective device against the effects of fumes/dust/aerosol. Keep unprotected persons away. Ensure adequate ventilation.Keep away from ignition sources. Protect from heat.Stop the spill, if possible. Contain spilled material by diking or using inert absorbent. Environmental precautions: Prevent from reaching drains, sewer or waterway. Collect contaminated soil for characterization per Section 13 Methods and material for containment and cleaning up: If in a laboratory setting, follow Chemical Hygiene Plan procedures.Place into properly labeled containers for recovery or disposal. If necessary, use trained response staff/contractor.Dust deposits should not be allowed to accumulate on surfaces, as these may form an explosive mixture if they are released into the atmosphere in sufficient concentration. Avoid dispersal of dust in the air (i.e., clearing dust surfaces with compressed air). Collect solids in powder form using vacuum with (HEPA filter) Reference to other sections: SECTION 7: Handling and storage Precautions for safe handling: Minimize dust generation and accumulation. Wash hands after handling. Avoid dispersal of dust in the air (i.e., clearing dust surfaces with compressed air). Routine housekeeping should be instituted to ensure that dusts do not accumulate on surfaces. Dry powders can build static electricity charges when subjected to the friction of transfer and mixing operations. Follow good hygiene procedures when handling chemical materials. Do not eat, drink, smoke, or use personal products when handling chemical substances. If in a laboratory setting, follow Chemical Hygiene Plan.Use only in well ventilated areas.Avoid generation of dust or fine particulate.Avoid contact with eyes, skin, and clothing. Conditions for safe storage, including any incompatibilities: Store in a cool location. Provide ventilation for containers. Avoid storage near extreme heat, ignition sources or open flame. Store away from foodstuffs. Store away from oxidizing agents.Store in cool, dry conditions in well sealed containers. Keep container tightly sealed.Store with like hazards Control Parameters: , , OSHA PEL TWA (Total Dust) 15 mg/m3 (50 mppcf*) , , ACGIH TLV TWA (inhalable particles) 10 mg/m3 SECTION 8: Exposure controls/personal protection Appropriate Engineering controls: Emergency eyewash fountains and safety showers should be available in the immediate vicinity of use/handling. Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapor or dusts (total/respirable) below the applicable workplace exposure limits (Occupational Exposure Limits-OELs) indicated above.Use under a fume hood. It is recommended that all dust control equipment such as local exhaust ventilation and material transport systems involved in handling of this product contain explosion relief vents or an explosion suppression system or an oxygen deficient environment.Ensure that dust-handling systems (such as exhaust ducts, dust collectors, vessels, and processing equipment) are designed in a manner to prevent the escape of dust into the work area (i.e., there is no leakage from the equipment). Respiratory protection: Not required under normal conditions of use. Use suitable respiratory protective device when high concentrations are present. Use suitable respiratory protective device when aerosol or mist is formed. For spills, respiratory protection may be advisable. Protection of skin: The glove material has to be impermeable and resistant to the product/ the substance/ the preparation being used/handled.Selection of the glove material on consideration of the penetration times, rates of diffusion and the degradation. Eye protection: Safety glasses with side shields or goggles. General hygienic measures: The usual precautionary measures are to be adhered to when handling chemicals. Keep away from food, beverages and feed sources. Immediately remove all soiled and contaminated clothing. Wash hands before breaks and at the end of work. Do not inhale gases/fumes/dust/mist/vapor/aerosols. Avoid contact with the eyes and skin. Appearance (physical state,color) : White solid Explosion limit lower : Explosion limit upper : Not Determined Not Determined Odor : Odorless Vapor pressure : 1 mmHg @ 865 C Odor threshold : Not Determined Vapor density : >1 pH-value : Not Determined Relative density : 1.987 Melting/Freezing point : 770 C Solubilities : Partly soluble Boiling point/Boiling range : 1420 C Partition coefficient (noctanol/water) : Not Determined Flash point (closed cup) : Not Determined Auto/Self-ignition temperature : Not Determined Evaporation rate : Not Determined Decomposition temperature : Not Determined Flammability (solid,gaseous) : Not Determined Viscosity : a. Kinematic:Not Determined b. Dynamic: Not Determined Density : Not Determined SECTION 9 : Physical and chemical properties SECTION 10 : Stability and reactivity Annexes 84 Reactivity: Nonreactive under normal conditions. Chemical stability: No decomposition if used and stored according to specifications.Hydroscopic. Possible hazardous reactions: Conditions to avoid: Store away from oxidizing agents, strong acids or bases.exposure to moist air or water.excess heat.Dust generation. Incompatible materials: Strong oxidizing agents.Bromine trifluoride. Hazardous decomposition products: Chlorine.oxides of potassium. Acute Toxicity : Oral : 2600 mg/kg Oral LD50 Rat Chronic Toxicity : No additional information. Corrosion Irritation : Dermal : Section 2 Classified as Skin Irritant Ocular : Section 2 Classified as eye irritant Sensitization : No additional information. Single Target Organ (STOT) : No additional information. Numerical Measures : No additional information. Carcinogenicity : IARC, NTP, OSHA: Not listed as carcinogen Mutagenicity : No additional information. Reproductive Toxicity : No additional information. Ecotoxicity Freshwater Fish : 96 Hr LC50 Lepomis macrochirus: 1060 mg/L Freshwater Fish : 96 Hr LC50 Pimephales promelas: 750 - 1020 mg/L Persistence and degradability : Not readily degradable in environment, except by dilution. Bioaccumulative potential : Mobility in soil : Partly soluble in water Other adverse effects : Causes dehydration following ingestion and/or changes in aquatic salinity levels, which may have deleterious effects on various aquatic, terrestrial or avian species. Waste disposal recommendations : Product/containers must not be disposed together with household garbage. Do not allow product to reach sewage system or open water.It is the responsibility of the waste generator to properly characterize all waste materials according to applicable regulatory entities (US 40CFR262.11). Consult federal state/ provincial and local regulations regarding the proper disposal of waste material that may incorporate some amount of this product. SECTION 11: Toxicological information SECTION 12: Ecological information SECTION 13: Disposal considerations UN-Number Not Regulated UN proper shipping name Not Regulated Transport hazard class(es) Packing group :Not Regulated Environmental hazard : Transport in bulk : Special precautions for user : United States (USA) SARA Section 311/312 (Specific toxic chemical listings) : Acute SARA Section 313 (Specific toxic chemical listings) : None of the ingredients is listed RCRA (hazardous waste code) : None of the ingredients is listed TSCA (Toxic Substances Control Act) : All ingredients are listed. CERCLA (Comprehensive Environmental Response, Compensation, and Liability Act) : None of the ingredients is listed Proposition 65 (California) : Chemicals known to cause cancer : None of the ingredients is listed Chemicals known to cause reproductive toxicity for females : None of the ingredients is listed Chemicals known to cause reproductive toxicity for males : None of the ingredients is listed Chemicals known to cause developmental toxicity : None of the ingredients is listed Canada Canadian Domestic Substances List (DSL) : All ingredients are listed. Canadian NPRI Ingredient Disclosure list (limit 0.1%) : None of the ingredients is listed Canadian NPRI Ingredient Disclosure list (limit 1%) : None of the ingredients is listed SECTION 14: Transport information SECTION 15: Regulatory information SECTION 16: Other information Annexes 2 This product has been classified in accordance with hazard criteria of the Controlled Products Regulations and the SDS contains all the information required by the Controlled Products Regulations.Note:. The responsibility to provide a safe workplace remains with the user.The user should consider the health hazards and safety information contained herein as a guide and should take those precautions required in an individual operation to instruct employees and develop work practice procedures for a safe work environment.The information contained herein is, to the best of our knowledge and belief, accurate.However, since the conditions of handling and use are beyond our control, we make no guarantee of results, and assume no liability for damages incurred by the use of this material.It is the responsibility of the user to comply with all applicable laws and regulations applicable to this material. GHS Full Text Phrases : Abbreviations and acronyms : IMDG: International Maritime Code for Dangerous Goods PNEC: Predicted No-Effect Concentration (REACH) CFR: Code of Federal Regulations (USA) SARA: Superfund Amendments and Reauthorization Act (USA) RCRA: Resource Conservation and Recovery Act (USA) TSCA: Toxic Substances Control Act (USA) NPRI: National Pollutant Release Inventory (Canada) DOT: US Department of Transportation IATA: International Air Transport Association GHS: Globally Harmonized System of Classification and Labelling of Chemicals ACGIH: American Conference of Governmental Industrial Hygienists CAS: Chemical Abstracts Service (division of the American Chemical Society) NFPA: National Fire Protection Association (USA) HMIS: Hazardous Materials Identification System (USA) WHMIS: Workplace Hazardous Materials Information System (Canada) DNEL: Derived No-Effect Level (REACH) Product name : Lithium Chloride, Reagent Manufacturer/Supplier Trade name : Manufacturer/Supplier Article number : S25389 Recommended uses of the product and uses restrictions on use : Manufacturer Details : AquaPhoenix Scientific 9 Barnhart Drive, Hanover, PA 17331 Supplier Details : Fisher Science Education 15 Jet View Drive, Rochester, NY 14624 Emergency telephone number : Fisher Science Education Emergency Telephone No.: 800-535-5053 Classification of the substance or mixture : Irr i tant Acute toxicity (oral, dermal, inhalation), category 4 Skin irritation, category 2 Eye irritation, category 2A Acute Oral Tox. 4 Skin Irrit. 2 Eye Irrit. 2A Signal word :Warning Hazard statements : Harmful if swallowed Causes skin irritation Causes serious eye irritation Precautionary statements : If medical advice is needed, have product container or label at hand Keep out of reach of children Read label before use Do not eat, drink or smoke when using this product Wash skin thoroughly after handling Wear protective gloves/protective clothing/eye protection/face protection IF SWALLOWED: Call a POISON CENTER or doctor/physician if you feel unwell Rinse mouth IF ON SKIN: Wash with soap and water IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses if present and easy to do. Continue rinsing If skin irritation occurs: Get medical advice/attention If eye irritation persists get medical advice/attention Take off contaminated clothing and wash before reuse SECTION 1: Identification of the substance/mixture and of the supplier SECTION 2: Hazards identification Annexes 2 Canadian NPRI Ingredient Disclosure list (limit 0.1%) : None of the ingredients is listed Canadian NPRI Ingredient Disclosure list (limit 1%) : None of the ingredients is listed This product has been classified in accordance with hazard criteria of the Controlled Products Regulations and the SDS contains all the information required by the Controlled Products Regulations.Note:. The responsibility to provide a safe workplace remains with the user.The user should consider the health hazards and safety information contained herein as a guide and should take those precautions required in an individual operation to instruct employees and develop work practice procedures for a safe work environment.The information contained herein is, to the best of our knowledge and belief, accurate.However, since the conditions of handling and use are beyond our control, we make no guarantee of results, and assume no liability for damages incurred by the use of this material.It is the responsibility of the user to comply with all applicable laws and regulations applicable to this material. GHS Full Text Phrases : Abbreviations and acronyms : IMDG: International Maritime Code for Dangerous Goods IATA: International Air Transport Association GHS: Globally Harmonized System of Classification and Labelling of Chemicals ACGIH: American Conference of Governmental Industrial Hygienists CAS: Chemical Abstracts Service (division of the American Chemical Society) NFPA: National Fire Protection Association (USA) HMIS: Hazardous Materials Identification System (USA) WHMIS: Workplace Hazardous Materials Information System (Canada) DNEL: Derived No-Effect Level (REACH) PNEC: Predicted No-Effect Concentration (REACH) CFR: Code of Federal Regulations (USA) SARA: Superfund Amendments and Reauthorization Act (USA) RCRA: Resource Conservation and Recovery Act (USA) TSCA: Toxic Substances Control Act (USA) NPRI: National Pollutant Release Inventory (Canada) DOT: US Department of Transportation SECTION 16 : Other information Product name : Hydrochloric Acid,ACS Manufacturer/Supplier Trade name : Manufacturer/Supplier Article number : S25358 Recommended uses of the product and uses restrictions on use : Manufacturer Details : AquaPhoenix Scientific 9 Barnhart Drive, Hanover, PA 17331 Supplier Details : Fisher Science Education 15 Jet View Drive, Rochester, NY 14624 Emergency telephone number : Fisher Science Education Emergency Telephone No.: 800-535-5053 Classification of the substance or mixture : Corrosive Serious eye damage, category 1 Corrosive to metals, category 1 Skin corrosion, category 1B Irritant Specific target organ toxicity following single exposure, category 3 Corr. Metals 1 Corr. Skin 1B Eye Damage 1 STOT. SE 3 Signal word :Danger Hazard statements : May be corrosive to metals Causes severe skin burns and eye damage May cause respiratory irritation Precautionary statements : If medical advice is needed, have product container or label at hand Keep out of reach of children Read label before use Use only outdoors or in a well-ventilated area Wear protective gloves/protective clothing/eye protection/face protection Keep only in original container Do not get in eyes, on skin, or on clothing Wash skin thoroughly after handling IF SWALLOWED: Rinse mouth. Do NOT induce vomiting SECTION 1: Identification of the substance/mixture and of the supplier SECTION 2: Hazards identification Annexes 4 IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses if present and easy to do. Continue rinsing Immediately call a POISON CENTER or doctor/physician Specific treatment (see supplemental first aid instructions on this label) Wash contaminated clothing before reuse Absorb spillage to prevent material damage Store in a well ventilated place. Keep container tightly closed Store locked up Store in corrosive resistant stainless steel container with a resistant inner liner Dispose of contents and container to an approved waste disposal plant Other Non-GHS Classification : WHMIS D1A E NFPA/HMIS NFPA SCALE (0-4) HMIS RATINGS (0-4) Ingredients: CAS 7647-01-0 Hydrochloric Acid, ACS 30-50 % CAS 7732-18-5 Water 50-70 % Percentages are by weight SECTION 4 : First aid measures Description of first aid measures After inhalation: Move exposed individual to fresh air. Loosen clothing as necessary and position individual in a comfortable position.Seek medical attention if irritation or coughing persists. After skin contact: Wash affected area with soap and water. Immediately remove contaminated clothing and shoes.Rinse thoroughly with plenty of water for at least 15 minutes.Immediately seek medical attention. After eye contact: Protect unexposed eye. Flush thoroughly with plenty of water for at least 15 SECTION 3: Composition/information on ingredients minutes.Remove contact lenses while rinsing.Continue rinsing eyes during transport to hospital. After swallowing: Rinse mouth thoroughly. Do not induce vomiting. Have exposed individual drink sips of water. Immediately seek medical attention. Most important symptoms and effects, both acute and delayed: Inhalation may cause irritation to nose and upper respiratory tract, ulceration, coughing, chest tightness and shortness of breath. Higher concentrations cause tachypnoea, pulmonary oedema and suffocation . Ingestion may cause corrosion of lips, mouth, oesophagus and stomach, dysphagia and vomiting.Pain, eye ulceration, conjunctival irritation, cataracts and glaucoma may occur following eye exposure.Erythema and skin irritation, as well as chemical burns to skin and mucous membranes may arise following skin exposure.;Potential sequelae following ingestion of hydrochloric acid include perforation, scarring of the oesophagus or stomach and stricture formation causing dysphagia or gastric outlet obstruction. In some cases, RADS may develop. Respiratory symptoms may take up to 36 hours to develop.Symptoms of burning sensation, cough, wheezing, laryngitis, shortness of breath, spasm, inflammation, edema of the larynx, spasm, inflammation and edema of the bronchi, pneumonitis, pulmonary edema. Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and skin. Indication of any immediate medical attention and special treatment needed: Provide SDS to Physician.Physician should treat symptomatically. SECTION 5 : Firefighting measures Extinguishing media Suitable extinguishing agents: Use water, dry chemical, chemical foam, carbon dioxide, or alcohol-resistant foam. For safety reasons unsuitable extinguishing agents: Special hazards arising from the substance or mixture: Combustion products may include carbon oxides or other toxic vapors.If in contact with metals toxic fumes may be released. Advice for firefighters: Protective equipment: Wear protective eyeware, gloves, and clothing. Refer to Section 8. Wear respiratory protection. Additional information (precautions): Thermal decomposition can produce poisoning chlorine. Hydrochloric acid reacts also with many organic materials with liberation of heat.Avoid inhaling gases, fumes, dust, mist, vapor, and aerosols. Avoid contact with skin, eyes, and clothing. SECTION 6 : Accidental release measures Personal precautions, protective equipment and emergency procedures: Ensure adequate ventilation. Ensure that air-handling systems are operational. Environmental precautions: Should not be released into environment. Prevent from reaching drains, sewer, or waterway. Methods and material for containment and cleaning up: Always obey local regulations. If necessary use trained response staff or contractor. Evacuate personnel to safe areas. Containerize for disposal. Refer to Section 13. Keep in suitable closed containers for disposal. Soak up with inert absorbent material and dispose of as hazardous waste. Cover spill with soda ash or calcium carbonate. Mix and add water to form slurry.Wear protective eyeware, gloves, and clothing. Refer to Section 8. Reference to other sections: SECTION 7 : Handling and storage Annexes 6 Precautions for safe handling: Prevent formation of aerosols. Never use hot water and never add water to the acid.Do not allow contact between hydrochloric acid, metal, and organics.Follow good hygiene procedures when handling chemical materials. Refer to Section 8. Prevent contact with skin, eyes, and clothing. Follow proper disposal methods. Refer to Section 13. Do not eat, drink, smoke, or use personal products when handling chemical substances. Use only in well ventilated areas.Avoid splashes or spray in enclosed areas. Conditions for safe storage, including any incompatibilities: Store in a cool location. Keep away from food and beverages. Protect from freezing and physical damage. Store away from incompatible materials. Provide ventilation for containers. Keep container tightly sealed.Containers for hydrochloric acid must be made from corrosion resistant materials: glass, polyethylene, polypropylene, polyvinyl chloride, carbon steel lined with rubber or ebonite. Control Parameters: 7647-01-0, Hydrochloric Acid, ACGIH: 2 ppm Ceiling 7647-01-0, Hydrochloric Acid, NIOSH: 5 ppm Ceiling; 7 mg/m3 Ceiling Appropriate Engineering controls: Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapor and mists below the applicable workplace exposure limits (Occupational Exposure Limits-OELs) indicated above. Emergency eye wash fountains and safety showers should be available in the immediate vicinity of handling. Respiratory protection: Not required under normal conditions of use. Where risk assessment shows air-purifying respirators are appropriate use a full-face particle respirator type N100 (US) or type P3 (EN 143) respirator cartridges as a backup to engineering controls. When necessary use NIOSH approved breathing equipment. Protection of skin: Select glove material impermeable and resistant to the substance. Select glove material based on rates of diffusion and degradation. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Use proper glove removal technique without touching outer surface. Avoid skin contact with used gloves. Wear protective clothing. Eye protection: Faceshield (8-inch minimum).Tightly fitting safety goggles. General hygienic measures: Perform routine housekeeping. Wash hands before breaks and immediately after handling the product. Avoid contact with skin, eyes, and clothing. Before rewearing wash contaminated clothing. Appearance (physical state,color) : Clear, colorless liquid. Explosion limit lower : Explosion limit upper : Non Explosive Non Explosive Odor : Pungent odor Vapor pressure : 5.7mmHg @ 0C Odor threshold : 0.3 – 14.9 mg/m3 Vapor density : 1.27 (Air=1) pH-value : < 1 Relative density : 1.0 - 1.2 SECTION 8 : Exposure controls/personal protection SECTION 9 : Physical and chemical properties Melting/Freezing point : - 74 C Solubilities : Miscible Boiling point/Boiling range : 81.5 - 110 C Partition coefficient (noctanol/water) : Not Determined Flash point (closed cup) : Not Applicable Auto/Self-ignition temperature : Not Determined Evaporation rate : >1.00 Decomposition temperature : Not Determined Flammability (solid,gaseous) : non combustible Viscosity : a. Kinematic:Not Determined b. Dynamic: Not Determined Density : Not Determined Hydrochloric Acid: MW is36.46 Reactivity: Reacts violently with bases and is corrosive. Chemical stability: No decomposition if used and stored according to specifications. Possible hazardous reactions: Attacks many metals in the presence of water forming flammable explosive gas (hydrogen).Reacts violently with oxidants forming toxic gas (chlorine). Conditions to avoid: Incompatible materials. Incompatible materials: Bases, Amines, Alkali metals, Metals, permanganates (potassium permanganate), Fluorine, Metal acetylides, Hexalithium disilicide. Hazardous decomposition products: Hydrogen chloride gas.Carbon oxides. Acute Toxicity : Inhalation : 7647-01-0 LD50 Rat 3124 ppm/hour Oral : 7647-01-0 LD50 Rat 238 - 277 mg/kg Dermal : 7647-01-0 LD50 Rabbit >5010 mg/kg Chronic Toxicity : No additional information. Corrosion Irritation : Dermal : 7647-01-0 Skin - rabbit Result: Causes burns. Ocular : 7647-01-0 Eyes - rabbit Result: Corrosive to eyes Sensitization : No additional information. Single Target Organ (STOT) : 7647-01-0: The substance or mixture is classified as specific target organ toxicant, single exposure, category 3 with respiratory tract irritation. Numerical Measures : No additional information. Carcinogenicity : No additional information. Mutagenicity : No additional information. SECTION 10 : Stability and reactivity SECTION 11 : Toxicological information Annexes 8 Ecotoxicity 7647-01-0 : Toxicity to fish LC50 - Gambusia affinis (Mosquito fish) - 282 mg/l - 96 h (Hydrochloric acid) Persistence and degradability : Bioaccumulative potential : Mobility in soil : Other adverse effects : Waste disposal recommendations : Do not allow product to reach sewage system or open water.It is the responsibility of the waste generator to properly characterize all waste materials according to applicable regulatory entities (US 40CFR262.11). Contact a licensed professional waste disposal service to dispose of this material. Dispose of empty containers as unused product. Product or containers must not be disposed together with household garbage. Chemical waste generators must determine whether a discarded chemical is classified as a hazardous waste. Chemical waste generators must also consult local, regional, and national hazardous waste regulations. Ensure complete and accurate classification. UN-Number 1789 UN proper shipping name HYDROCHLORIC ACID Transport hazard class(es) Class: 8 Corrosive substances Packing group :II Environmental hazard : Transport in bulk : Special precautions for user : United States (USA) SARA Section 311/312 (Specific toxic chemical listings) : Acute SARA Section 313 (Specific toxic chemical listings) : 7647-01-0 Hydrochloric Acid RCRA (hazardous waste code) : None of the ingredients is listed TSCA (Toxic Substances Control Act) : All ingredients are listed. SECTION 12 : Ecological information SECTION 13 : Disposal considerations SECTION 14 : Transport information SECTION 15 : Regulatory information CERCLA (Comprehensive Environmental Response, Compensation, and Liability Act) : 7647-01-0 Hydrochloric Acid 5000 lbs Proposition 65 (California) : Chemicals known to cause cancer : None of the ingredients is listed Chemicals known to cause reproductive toxicity for females : None of the ingredients is listed Chemicals known to cause reproductive toxicity for males : None of the ingredients is listed Chemicals known to cause developmental toxicity : None of the ingredients is listed Canada Canadian Domestic Substances List (DSL) : All ingredients are listed. Canadian NPRI Ingredient Disclosure list (limit 0.1%) : None of the ingredients is listed Canadian NPRI Ingredient Disclosure list (limit 1%) : 7647-01-0 Hydrochloric Acid This product has been classified in accordance with hazard criteria of the Controlled Products Regulations and the SDS contains all the information required by the Controlled Products Regulations.Note:. The responsibility to provide a safe workplace remains with the user.The user should consider the health hazards and safety information contained herein as a guide and should take those precautions required in an individual operation to instruct employees and develop work practice procedures for a safe work environment.The information contained herein is, to the best of our knowledge and belief, accurate.However, since the conditions of handling and use are beyond our control, we make no guarantee of results, and assume no liability for damages incurred by the use of this material.It is the responsibility of the user to comply with all applicable laws and regulations applicable to this material. GHS Full Text Phrases : Abbreviations and acronyms : IMDG: International Maritime Code for Dangerous Goods PNEC: Predicted No-Effect Concentration (REACH) CFR: Code of Federal Regulations (USA) SARA: Superfund Amendments and Reauthorization Act (USA) RCRA: Resource Conservation and Recovery Act (USA) TSCA: Toxic Substances Control Act (USA) NPRI: National Pollutant Release Inventory (Canada) DOT: US Department of Transportation IATA: International Air Transport Association GHS: Globally Harmonized System of Classification and Labelling of Chemicals ACGIH: American Conference of Governmental Industrial Hygienists CAS: Chemical Abstracts Service (division of the American Chemical Society) NFPA: National Fire Protection Association (USA) SECTION 16 : Other information HMIS: Hazardous Materials Identification System (USA) WHMIS: Workplace Hazardous Materials Information System (Canada) DNEL: Derived No-Effect Level (REACH) Annexes 8 1.1 Product identifiers Product name : Poly(allylamine hydrochloride) Product Number : Brand : 283223 Aldrich Index-No. : 612-191-00-3 CAS-No. : 71550-12-4 1.2 Relevant identified uses of the substance or mixture and uses advised against Identified uses : Laboratory chemicals, Manufacture of substances 1.3 Details of the supplier of the safety data sheet Company : Sigma-Aldrich Company Ltd. The Old Brickyard NEW ROAD, GILLINGHAM Dorset SP8 4XT UNITED KINGDOM Telephone : +44 (0)1747 833000 Fax : +44 (0)1747 833313 E-mail address : [email protected] 1.4 Emergency telephone number Emergency Phone # : +44 (0)870 8200418 (CHEMTREC) 1.1 Classification of the substance or mixture Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Skin sensitization (Category 1) Acute toxicity, Oral (Category 4) Classification according to EU Directives 67/548/EEC or 1999/45/EC May cause sensitization by skin contact. Harmful if swallowed. 1.2 Label elements Labelling according Regulation (EC) No 1272/2008 [CLP] Pictogram Signal word Warning Hazard statement(s) H302 Harmful if swallowed. H317 May cause an allergic skin reaction. Precautionary statement(s) P280 Wear protective gloves. Supplemental Hazard Statements none SECTION 1: Identification of the substance/mixture and of the supplier SECTION 2: Hazards identification According to European Directive 67/548/EEC as amended. Hazard symbol(s) R-phrase(s) R22 Harmful if swallowed. R43 May cause sensitization by skin contact. S-phrase(s) S36/37 Wear suitable protective clothing and gloves. 1.1 Substances Formula : C3H8ClN Component Concentration Allylamine, hydrochloride, homopolymer CAS-No. 71550-12-4 EC-No. 415-050-2 Index-No. 612-191-00-3 - SECTION 4: First aid measures 1.5 Description of first aid measures General advice Consult a physician. Show this safety data sheet to the doctor in attendance. If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician. In case of skin contact Wash off with soap and plenty of water. Consult a physician. In case of eye contact Flush eyes with water as a precaution. If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician. 1.6 Most important symptoms and effects, both acute and delayed To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated. 1.7 Indication of any immediate medical attention and special treatment needed no data available SECTION 5: Firefighting measures 1.8 Extinguishing media Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide. 1.9 Special hazards arising from the substance or mixture Carbon oxides, nitrogen oxides (NOx), Hydrogen chloride gas 1.10 Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary. 1.11 Further information no data available SECTION 6: Accidental release measures SECTION 3: Composition/information on ingredients Annexes 10 1.12 Personal precautions, protective equipment and emergency procedures Use personal protective equipment. Avoid dust formation. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Avoid breathing dust. 1.13 Environmental precautions Do not let product enter drains. 1.14 Methods and materials for containment and cleaning up Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed containers for disposal. 1.15 Reference to other sections For disposal see section 13. SECTION 7: Handling and storage 1.16 Precautions for safe handling Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Provide appropriate exhaust ventilation at places where dust is formed. 1.17 Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place. strongly hygroscopic Handle and store under inert gas. 1.18 Specific end uses no data available Control Parameters: 7647-01-0, Hydrochloric Acid, ACGIH: 2 ppm Ceiling 7647-01-0, Hydrochloric Acid, NIOSH: 5 ppm Ceiling; 7 mg/m3 Ceiling Appropriate Engineering controls: Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapor and mists below the applicable workplace exposure limits (Occupational Exposure Limits-OELs) indicated above. Emergency eye wash fountains and safety showers should be available in the immediate vicinity of handling. Respiratory protection: Not required under normal conditions of use. Where risk assessment shows air-purifying respirators are appropriate use a full-face particle respirator type N100 (US) or type P3 (EN 143) respirator cartridges as a backup to engineering controls. When necessary use NIOSH approved breathing equipment. Protection of skin: Select glove material impermeable and resistant to the substance. Select glove material based on rates of diffusion and degradation. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Use proper glove removal technique without touching outer surface. Avoid skin contact with used gloves. Wear protective clothing. Eye protection: Faceshield (8-inch minimum).Tightly fitting safety goggles. General hygienic measures: Perform routine housekeeping. Wash hands before breaks and immediately after handling the product. Avoid contact with skin, eyes, and clothing. Before rewearing wash contaminated clothing. Appearance (physical state,color) : solid Explosion limit lower : Explosion limit upper : no data available SECTION 8: Exposure controls/personal protection SECTION 9 : Physical and chemical properties Odor : no data available Vapor pressure : no data available Odor threshold : no data available Vapor density : no data available pH-value : no data available Relative density : no data available Melting/Freezing point : no data available Solubilities : no data available Boiling point/Boiling range : no data available Partition coefficient (noctanol/water) : no data available Flash point (closed cup) : no data available Auto/Self-ignition temperature : no data available Evaporation rate : no data available Decomposition temperature : no data available Flammability (solid,gaseous) : no data available Viscosity : no data available Density : Not Determined 1.1 Reactivity no data available 1.2 Chemical stability no data available 1.3 Possibility of hazardous reactions no data available 1.4 Conditions to avoid Avoid moisture. 1.5 Incompatible materials Strong oxidizing agents 1.6 Hazardous decomposition products Other decomposition products - no data available . Acute Toxicity : Oral : 2600 mg/kg Oral LD50 Rat Chronic Toxicity : No additional information. Corrosion Irritation : Dermal : Section 2 Classified as Skin Irritant Ocular : Section 2 Classified as eye irritant Sensitization : No additional information. Single Target Organ (STOT) : No additional information. Numerical Measures : No additional information. SECTION 10 : Stability and reactivity SECTION 11: Toxicological information Annexes 12 Carcinogenicity : IARC, NTP, OSHA: Not listed as carcinogen Mutagenicity : No additional information. Reproductive Toxicity : No additional information. 1.1 Information on toxicological effects Acute toxicity no data available Skin corrosion/irritation no data available Serious eye damage/eye irritation no data available Respiratory or skin sensitization May cause allergic skin reaction. Germ cell mutagenicity no data available Carcinogenicity IARC: No component of this product present at levels greater than or equal to 0.1% is identified as probable, possible or confirmed human carcinogen by IARC. Reproductive toxicity no data available Specific target organ toxicity - single exposure no data available Specific target organ toxicity - repeated exposure no data available Aspiration hazard no data available Potential health effects Inhalation May be harmful if inhaled. May cause respiratory tract irritation. Ingestion Harmful if swallowed. Skin May be harmful if absorbed through skin. May cause skin irritation. Eyes May cause eye irritation. Signs and Symptoms of Exposure To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated. Additional Information RTECS: Not available 1.1 Waste treatment methods Product Offer surplus and non-recyclable solutions to a licensed disposal company. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. Contaminated packaging Dispose of as unused product. 1.1 UN number SECTION 14: Transport information SECTION 12: Ecological information SECTION 13: Disposal considerations ADR/RID: - IMDG: - IATA: - 1.2 UN proper shipping name ADR/RID: Not dangerous goods IMDG: Not dangerous goods IATA: Not dangerous goods 1.3 Transport hazard class(es) ADR/RID: - IMDG: - IATA: - 1.4 Packaging group ADR/RID: - IMDG: - IATA: - 1.5 Environmental hazards ADR/RID: no IMDG Marine pollutant: no IATA: no 1.6 Special precautions for user no data available This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006. 1.1 Safety, health and environmental regulations/legislation specific for the substance or mixture no data available 1.2 Chemical Safety Assessment no data available Further information Copyright 2012 Sigma-Aldrich Co. LLC. License granted to make unlimited paper copies for internal use only. The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Corporation and its Affiliates shall not be held liable for any damage resulting from handling or from contact with the above product. See www.sigmaaldrich.com and/or the reverse side of invoice or packing slip for additional terms and conditions of sale. SECTION 15: Regulatory information SECTION 16: Other information Annexes 14