/Producer(Sub Systems, Inc.)/CreationDate(D:20211226234727+05'00')/ModDate(D:20211226234727+05'00')/Creator(Sub Systems, Inc.) Because of this latter factor, some sulfanilamide will remain dissolved in the mother liquor (the liquid remaining after crystallization has taken place). The pure sample had a melting range of 162.9 C to 165.8 C while the impure sample had a melting range of 160.3 C to 163.2 C as shown in Table 1. Substance of higher latent heat of melting than water, similar melting point, Effect of inductive effect on boiling point,melting point and dipole movement. The melting point of ice decreases from 0 C to -22 C on mixing salt in it in proper proportion. had a melting range of 162 C to 165 C while the impure sample had a melting range of If unknown C was acetylsalicylic acid, then the melting point of the mixture should have been relatively close to the melting range of acetylsalicylic acid, 138 C to 140C. utilized to verify the purity of the final material. May cause respiratory tract irritation. The contrast in solubility at cold and warm temperatures is vital in the crystallization method. At the option of the instructor, turn in your crystallized material in a properly labeled container, Preparations. This is true for several reasons: experimental loss, the original sample is not 100% sulfanilamide, and some sulfanilamide is soluble in the solvent even at 0 C. 607 pp., illustrated. slightly Acidity of alcohols and basicity of amines. It has a density of 1.08 g/cm 3 and a melting point of 164.5-166.5 C. Then, the properties of 3 different solvents, water, methyl alcohol, and toluene, were analyzed to determine the most appropriate solvent for the crystallization of an impure sample of organic compound, fluorene. The paragraph is therefore a tad confusing. An impure sample will have a lower melting point and the range will be bigger. Therefore ethyl alcohol since they have similar polarities. affinity for the solvent at a higher temperature. Crystallization methods are designed to produce a supersaturated solution that eventually forms crystals. Biphenyl. consists of two covalently attached benzene rings, and as a result we closely resemble the The melting point of a substance decreases with increase in presence of impurities in it. You will crystallize a sample of impure sulfanilamide by dissolving it in the minimum amount of boiling 95% ethyl alcohol (78 C) and then cooling the solution, first to room temperature, and then to 0 C in an ice-water bath. 74 -116. Create three research questions that would be appropriate for a historical analysis essay, keeping in mind the characteristics of a critical r, Carbon Cycle Simulation and Exploration Virtual Gizmos - 3208158, 1.1 Functions and Continuity full solutions. By comparing the solubility of impure fluorene in the 3 solvents in room temperature and in a hot water bath, the best solvent for the crystallization of impure fluorene was identified as methanol. is a hazard so this is a concern. The first 5 pages are background explanation. The purity of the pure sample was also confirmed using the melting point technique. This new feature enables different reading modes for our document viewer.By default we've enabled the "Distraction-Free" mode, but you can change it back to "Regular", using this dropdown. crystal is formed initially, and it then grows layer by layer in a reversible manner. was either acetylsalicylic acid, with the melting point ranges of 138 to 140, or benzoin, with Critical thinking (D): The best crystallization solvent is the solvent that does not Also, compare these to the literature value. Part A: Table 1. Note that impurities in a solid will affect the melting point, but the freezing point depression effect (a colligative effect) has to do with impurities in the liquid phase, not in the solid. Connect and share knowledge within a single location that is structured and easy to search. [19], In 1937, Elixir sulfanilamide, a medicine consisting of sulfanilamide dissolved in diethylene glycol poisoned and killed more than 100 people as a result of acute kidney failure, prompting new US regulations for drug testing. Purpose: in this experiment we will get introduced to the technique of crystallization. However, if the observed melting temperatures are outside of this range, then the compound is not pure. Report the melting points for both the impure sulfanilamide and the crystallized sulfanilamide and comment on the differences. Hypothesis: crystallization will be used to purify the desired compound and isolate solid. In this case, water was too polar for fluorene to dissolve even at a high temperature while toluene was too nonpolar that fluorene dissolved easily at room temperature. Introduction. When melting point ranges were compared, it was assumed that unknown C For example: Melting Range 6 . O Urea Water or Hexane NH 2 O H 2 N 5. Crystallization is an equilibrium process and produces very pure material. One way to deal with it is to physically remove the ice but this is very difficult. In Part C of this experiment, we will determine the identity of an. There are several ways to determine the melting point of a compound, including using a melting point apparatus. organic compounds from a mixture of compounds we are given a chemical in liquid isolated should have been a very small amount, as not much impurity should be soluble in find the appropriate solvent for crystallization and then perform it on the fluorine sample Mass of watch glass + Pure fluorene g 48. This microscopic melting is not visible to the eye. also the first generation of antibiotics, used to treat many diseases. While the pure sample lied within the primary melting range of sulfanilamide, there was a depression in the melting range of the impure sample because impurities disrupted the crystal lattice energies. affinity for molecules of its own kind than for the impurities, they leave behind the impurities [5], Since sulfanilamide is used almost exclusively in topical vaginal preparations these days, adverse effects are typically limited to hypersensitivity or local skin reactions. temperatures. crystallization solvent for fluorene, impure fluorene is dissolved in methyl alcohol at its [5], InChI=1S/C6H8N2O2S/c7-5-1-3-6(4-2-5)11(8,9)10/h1-4H,7H2,(H2,8,9,10). If you have an ice bath the temperature is zero deg C until all the ice melts but if you had salt and mix there is a fall in temperature. Although all samples start melting at the eutectic temperature, the first droplet of liquid is not seen until approximately \(10\)-\(20\%\) of the sample has microscopically melted. By clicking Post Your Answer, you agree to our terms of service, privacy policy and cookie policy. Cholesterol, mostly non polar, very slightly polar. Market-Research - A market research for Lemon Juice and Shake. For most substances, the Thus ice problem when driving is solved (aside from the environmental concern of all the heavy salts). Report the melting points for both the impure sulfanilamide and the crystallized sulfanilamide and comment on the differences. Any differences, numerically, may have been to calibration settings of the Differences between Create three research questions that would be appropriate for a historical analysis essay, keeping in mind the characteristics of a critical r, Carbon Cycle Simulation and Exploration Virtual Gizmos - 3208158, 1.1 Functions and Continuity full solutions. : an American History (Eric Foner), Forecasting, Time Series, and Regression (Richard T. O'Connell; Anne B. Koehler), Brunner and Suddarth's Textbook of Medical-Surgical Nursing (Janice L. Hinkle; Kerry H. Cheever), Campbell Biology (Jane B. Reece; Lisa A. Urry; Michael L. Cain; Steven A. Wasserman; Peter V. Minorsky), Psychology (David G. Myers; C. Nathan DeWall), Chemistry: The Central Science (Theodore E. Brown; H. Eugene H LeMay; Bruce E. Bursten; Catherine Murphy; Patrick Woodward). When working with organic compounds in a lab, the purity of the compound can be partially determined through the use of a precise measurement of the melting point. Making statements based on opinion; back them up with references or personal experience. The three solvents will illustrate three very different solubility behaviors: On the other hand, the solubility of a compound decreases as a solutions cool. Lesson 8 Faults, Plate Boundaries, and Earthquakes, Copy Of Magnetism Notes For Physics Academy Lab of Magnetism For 11th Grade, Chapter 02 Human Resource Strategy and Planning, Week 1 short reply - question 6 If you had to write a paper on Title IX, what would you like to know more about? Copyright 2023 StudeerSnel B.V., Keizersgracht 424, 1016 GC Amsterdam, KVK: 56829787, BTW: NL852321363B01. Some of the deductions in the percentage of recovery were due to the impurities being left behind in the mother liquor and others were due to the use of too much solvent in the process of dissolving the solid with heat because the solid compounds have a higher affinity for the solvent at a higher temperature. However, the melting point of impure sulfanilamide may be different due to the presence of impurities. Also, compare these to the literature value. By comparing the solubility of impure fluorene in the 3 solvents in room, temperature and in a hot water bath, the best solvent for the crystallization of im, 0.519 g was collected, with a 69.57% recovery of sulfanilamide as shown in, Crystallization is a method of separation centered on the reduced solubili, a certain solvent at a specific temperature or pressure. The melting point of the mixture of the two compounds came out to be 122.4 C as shown in Table 7. endobj Accessibility StatementFor more information contact us atinfo@libretexts.orgor check out our status page at https://status.libretexts.org. In this section is described the theory behind the phenomenon of melting point depression (which is identical to freezing point depression since freezing and melting are the same processes in reverse) and why an impure sample has a broad melting range. The melting point technique was also utilized to determine the purity of the pure sample of both sulfanilamide and fluorene. within its primary melting point range. $_|tj\*9~i7QYfEyn{9O>!53,;{w/_T'c3mXG/YPoAl?n'h 2 0 obj Melting point : 165 - 166 C : Freezing point : No data available : Boiling point : No data available : Flash point : No data available : Auto-ignition temperature : No data available : Unknown C by itself had a melting range of 138. By using the recrystallization technique and observing its appearance and finding Its melting point, a purer form of sulfanilamide would be obtained. >> The melting point of the impure sulfanilamide was 165. true /ColorSpace 12 0 R /SMask 13 0 R /BitsPerComponent 8 /Filter /FlateDecode However, the melting point of impure sulfanilamide may be different due to the presence of impurities. Finally, unknown C was identified as benzoin through melting point technique analysis. In 1938, the Food, Drug and Cosmetic Act was passed. May cause methemoglobinemia, cyanosis, convulsions, and death. That is why salt is added to make freezing mixtures to keep ice creams frozen. To begin, 2.5 grams of impure acetanilide will be obtained from the teacher's assistant. It is important to accurately determine the melting point of a compound, especially in the pharmaceutical industry, to ensure the safety and effectiveness of the final product. Stack Exchange network consists of 181 Q&A communities including Stack Overflow, the largest, most trusted online community for developers to learn, share their knowledge, and build their careers. The melting point of a substance is often used to determine purity. |(B8)[IqZ/gR 1%Q,#>Z;SstBnHs.pY'(k8Vjl[h /0uO *~#PTdkTK0H[3XQ_R1QH`;JCV4:ZHzbx4S0vg),+3 It has a max of 255 and 312 nm. Compound B will continue to dissolve in the melt, until it reaches the eutectic composition (point a in Figure 6.7b), and the system will continue to melt at this composition until the entirety of the minor component (the impurity) is dissolved. I hope you get it. Although microscopic melting begins at the eutectic temperature, the first value of the melting range (when a droplet of liquid is seen with the eye) is not necessarily recorded at this temperature. We are expected to The pure sample Acetylsalicylic Acid 138-. On the other hand, the solubility of a The melting point of the impure sulfanilamide was 1650 1685 C which was lower. There are several polar bonds in sulfanilamide, the NH and the SO bonds. state, it will be converted into a solid crystalline state. We know that fluorene is non-polar so as like dissolves like it will be The solid must be heated to a certain temperature in order for this structure to be disrupted and for the solid to melt. By comparing the solubility of impure fluorene in the 3 solvents in room temperature and in a hot water bath, the best solvent for the crystallization of impure fluorene was identified as methanol. Discussion: The melting point of the impure sulfanilamide was 153-158 degrees However, there is a more significant difference in entropy between a pure and impure liquid, and an impure liquid has greater disorder and greater entropy. The final value of the melting range is at the highest the melting point of the pure solid, but is often lower, reflecting the depressed melting point of the bulk solid. at the same time. Acetaminophen is moderately polar meaning it is soluble in ethanol, poorly soluble in Introduction: The system follows the melting line in Figure 6.7b either to the left or right of the eutectic temperature (depending on which side of the eutectic point is started), adjusting its melting temperature as the bulk component increases its concentration in the melt. The melting point of a compound is a measure of its purity. Through crystallization of 0.746 g of fluorene using methanol as the solvent, 0.468 g of pure fluorene sample was extracted, with a 62.73% recovery as shown in Table 4. The melting point is recorded as the temperature at which the compound transitions from a solid to a liquid. The first number is the temperature at which the substance begins to melt (when liquid is first observed) and the second number is the temperature at which the sample has completely melted (no solid left). Because of these bonds, sulfanilamide has some polar character. A larger \(\Delta S^\text{o}\) means that a smaller temperature will be required to "match" the enthalpy component. nwC0\a`qPi+^9o}'w^OX"nlngH5wCF-?n&Tmc5{9 Please see attached lab report. Sulfanilamide initially has a melting range of 163 to 166. 151 168-172 Practically Melting point of impure sulfanilamide = 165.1 C Melting point of crystallised sulfanilamide = 163.0 C There is difference between melting points of crude and crystalline sulfanilamide that is because recrystallised product has a high purity or it doesn't have impurities and crude sulfanilamide or impure sulfanilamide has impurities in it. Furthermore, the melting points of the pure compounds were close to the literature ones. terms of purifying an impure sample of a compound, crystallized molecules have a greater Please see attached lab report. unknown using the melting point technique. Based on the melting point of the crystallized sulfanilamide, it is more pure than the impure sample, but it is not certain whether it is 100% pure sulfanilamide. Given Melting Ranges of Known Compounds, Unknown C (0.1 g) + Acetylsalicylic Acid (0.1 g), In this experiment, crystallization was conducted to purify an impure sample of, sulfanilamide using a known solvent, 95% ethyl alcohol, and melting point techni. In flammable, O-toluic acid (CH 3 )C 6 H 4 ( The melting point technique was useful in this sense because if An impure substance cannot have a definite melting point, as it depends on the degree of impurity. Melting point depression occurs due to the nature of a material's solid state. This continues until the entire sample is melted. For example, a solid that is \(20\%\) compound A and \(80\%\) compound B would have a final melting temperature of point c in Figure 6.7b. That is why salt is added to make freezing mixtures to keep ice creams frozen. . 113C. Compound Melting Range (C) Finally, unknown C was identified as benzoin through melting I need help on the last 3 pages. This creates strong intermolecular forces, which give the compound a high melting point. Calculating probabilities from d6 dice pool (Degenesis rules for botches and triggers). Through the crystallization of impure sulfanilamide and fluorene, pure sulfanilamide and fluorene was recovered. ;fj ^U|Y_e,s#!f18p `g]mr}?R1 okvA. Percent Recovery of Pure Sulfanilamide through Crystallization and Melting In other words if you add salt to ice that is homogeneously right at the freezing point you won't get liquid water below zero because there is no where for the heat to flow. Depending on the quantity of impurity, the system may have progressed far from the eutectic temperature (perhaps to point b in Figure 6.7b) before liquid becomes visible to the eye. [5], Sulphanilamide is contraindicated in those known to be hypersensitive to sulfonamides, in nursing mothers, during pregnancy near term and in infants less than 2 months of age. sulfanilamide. ]0%vAK3>0^efPV{LzPe't>H)1StNiWy2^bT)fb6;MFd`B-&f3hVMO2qKAUj5_1m*jbgPST+|J p|\8PxW_( W,Up2"y o9N3A|>Iml&M;9p Y`t&$S)5L.Hjf B%G4b1=h:7r3 " lAQ,N;d tE`JNhfR8ADJjGB&K4I;Ni&@V0]EcQ,`x}:A?H^-7rna6hgrJi#Mbb&. Unknown C 138- [comments by Buck Thorn] Note that impurities in a solid will affect the melting point, but the freezing point depression effect (a colligative effect) has to do with impurities in the liquid phase, not in the solid. Melting Point Range of Impure Sample (C) 110-113. The melting point of a sample is usually expressed as two numbers called the melting point range, such as 112 - 114C. Based on the melting point of the crystallized sulfanilamide, it is more By clicking Accept all cookies, you agree Stack Exchange can store cookies on your device and disclose information in accordance with our Cookie Policy. Sulfanilamide is one of the sulfa drugs, the first generation of antibiotics to be used in successfully treating many major diseases such as malaria, tuberculosis, and leprosy. It has a max of 255 and 312nm. The purified substance can then be separated from the solvent and impurities by filtration. In part B, by comparing the solubility of impure fluorene in the 3 solvents in room temperature and in a hot water bath, the best solvent for the crystallization of impure fluorene was identified as methanol, as shown in Table 3, because fluorene was only partially soluble in methanol in room temperature and completely soluble in methanol at a higher temperature. To subscribe to this RSS feed, copy and paste this URL into your RSS reader. In addition, the best solvent for recrystallizing an unknown solid will be determined and identified . The temperature is then slowly increased until the compound melts. Une chimie qui gurit: Histoire de la dcouverte des sulfamides. Asking for help, clarification, or responding to other answers. 178 101 Irritant; 386 148 Low The purpose of mixing salt to ice is to get a simple way to obtain a temperature lower the 0C without a fridge. Melting Points. Crystallization methods are designed to ous. Is it possible to create a concave light? In this case pure water at this temperature will be in the solid phase and exist as ice because the surrounding temperature is lower than the melting/freezing point. However, there was a depression in the melting point of the mixture, Some of the deductions in the percentage of recovery were due to the impurities being left behind in the mother liquor and others were due to the use of too much solvent in the process of dissolving the solid with heat because the solid compounds have a higher affinity for the solvent at a higher temperature. Specifically in this experiment, the temperature was adjusted to affect the solubility. For the ice cream making process, we start with pure ice and have the impurity in the liquid. point of the solute so that the solute is not melted before the solvent reaches its boiling sul- fanilamide in 95% ethyl alcohol as the solvent. [15] It was patented in 1909. Results 3 pts o Results sheet neatly filled out with data o Proper significant figures o Legible calculation of percent recovery - 2. The general technique involves dissolving the material to be crystallized in a hot solvent and cooling the solution slowly. Urea is highly polar, soluble in water, poorly soluble in hexane and crystallisable in In this experiment, crystallization was conducted to purify an impure sample of << /Type /Page /Parent 3 0 R /Resources 6 0 R /Contents 4 0 R /MediaBox [0 0 612 792] Which would burn you faster? At roughly what temperature will crystals of A appear? But there was a problem. The solubility of sulfanilamide in 95% ethyl alcohol is given in the following table: Notice that the solubility increases significantly as the temperature increases. literature value. How many grams of A would come out of solution? I need help on the last 3 pages. The higher the concentration of the impurities, the more anomalous the melting point.. The literature melting point of pure sulfanilamide Is 164. Pure and Impure Samples of Fluorene. Originally, fluorene has a melting range of 116C to 117C. Impurities can be introduced into the compound during its synthesis or during its handling and storage. When a compound is pure, its molecules are all arranged in an orderly, repeating pattern. When an impure solid is warmed, microscopic melting first occurs in a pure region by the component with the lower melting point (compound A in Figure 6.7a). endobj An impure solid is typically heterogeneous on the microscopic level, with pure regions of each component distributed through the bulk solid much like granite. The pH of a 0.5% aqueous solution of Sulfanilamide is 5.8 to 6.1. Sulfanilamide 165-167 2-Aminophenol 174 4-Toluic acid 180 . Posted 4 months ago View Answer Q: What compounds does the mother liquor contain? The identity of unknown C was narrowed down to a single compound by collecting the melting range of a compound consisting of unknown C and acetylsalicylic acid. When an impure solid is warmed, microscopic melting first occurs in a pure region by the component with the lower melting point (compound A in Figure 6.7a). Benzyl alcohol is not the right choice for the solvent since it's boiling point is 205oC, Biphenyl is very similar in structure to benzene and has very similar polarities. Once the minor component is completely dissolved, further melting continues of the bulk component. Has 90% of ice around Antarctica disappeared in less than a decade? Avoid contact with skin and eyes. Browse other questions tagged, Start here for a quick overview of the site, Detailed answers to any questions you might have, Discuss the workings and policies of this site. Part C: Table 6. Where does this (supposedly) Gibson quote come from? To use this instrument, a small amount of the compound is placed in a capillary tube, which is then inserted into the apparatus. It is also known as 4-aminobenzenesulfonamide or 4-aminobenzenesulphonamide. I have also typed in red where I need help. << /Length 5 0 R /Filter /FlateDecode >> Ref: Hansch,C et al. In terms of purifying an impure sample of a compound, crystallized molecules have a greater affinity for molecules of its own kind than for the impurities, they leave behind the impurities initially existent in the compound in the mother liquor, to ultimately yield relatively pure crystals. The preliminary melting of compound A in Figure 6.7a forms tiny pools of liquid that begin to dissolve compound B from the bulk solid. For driving and general transport, ice on the roads/walkways, etc. The best answers are voted up and rise to the top, Not the answer you're looking for? This page titled 6.1C: Melting Point Theory is shared under a CC BY-NC-ND 4.0 license and was authored, remixed, and/or curated by Lisa Nichols via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request. Try it at home Mixing salt will result in liquid water that can stay liquid below $0^oC$. seeing if the mp width is less than 2.0 which shows purity, but any larger than that it's impure. Of that sample, 0.1 grams will be saved for a melting point determination. So, salt is added to the cooling mixture and (supposedly) not to the recipe's ingredients. the mother liquid. pdf, Applying the Scientific Method - Pillbug Experiment, Leadership class , week 3 executive summary, I am doing my essay on the Ted Talk titaled How One Photo Captured a Humanitie Crisis https, School-Plan - School Plan of San Juan Integrated School, SEC-502-RS-Dispositions Self-Assessment Survey T3 (1), Techniques DE Separation ET Analyse EN Biochimi 1. A mathematical description is in Figure 6.8b: as \(\Delta S^\text{o}\) is the denominator in the final equation, a larger \(\Delta S^\text{o}\) corresponds to a smaller \(T_\text{melting}\). The melting point of pure sulfanilamide is around 303-305C. Ref: MERCK INDEX 1976 Water Sol Estimate from Fragments: Wat Sol v1. Melting of a pure solid occurs at a higher temperature than melting of an impure solid, a concept called melting point depression (or freezing point depression). 3, acetaminophen C 8 H 9 NO 2 NIST Spectra Density: 1. The process of melting the ice cools down the ice/salt water mixture. Thanks for contributing an answer to Chemistry Stack Exchange! water bath. Percent Recovery of Pure Sulfanilamide through Crystallization and Melting Ranges of Pure and Impure Samples of Sulfanilamide, Impure sulfanilamide had a yellow/white color, Mass of watch glass + Pure sulfanilamide (g), Melting Point Range of Impure Sample (C). In part A, 0. experiment, the temperature was adjusted to affect the solubility. : an American History (Eric Foner), Forecasting, Time Series, and Regression (Richard T. O'Connell; Anne B. Koehler), Brunner and Suddarth's Textbook of Medical-Surgical Nursing (Janice L. Hinkle; Kerry H. Cheever), Campbell Biology (Jane B. Reece; Lisa A. Urry; Michael L. Cain; Steven A. Wasserman; Peter V. Minorsky), Psychology (David G. Myers; C. Nathan DeWall), Chemistry: The Central Science (Theodore E. Brown; H. Eugene H LeMay; Bruce E. Bursten; Catherine Murphy; Patrick Woodward), Lecture notes, lecture all - Chapter 15-20, Determination of the Alcohol Content of Wine by Fractional Distillation Lab Report, Study Guide for Exam #1 Chapter 1- 4 for ECON 2. As shown in Table 4, a pure sample collected through crystallization was relatively pure, with a melting range of 116.3C to 117.8C. The melting point of a substance is often used to determine purity. The melting point of a compound is a measure of its purity. ethanol. My point is you actually WANT the ice to melt into a salt solution, because that will better cool the churn - as long as there's enough salt so that the liquid is cold enough. irritant. When melting point ranges were compared, it was assumed that unknown C was either acetylsalicylic acid, with the melting point ranges of 138 to 140, or benzoin, with the melting point ranges of 135 to136. be 122 C as shown in Table 7. Please find attached the modified lab report. You will also weigh your sample and calculate the percent recovery. may have been to some of the product still being soluble in the solvent, even in the ice 114cY uKG'G*7:~u9>Zi`= t8$DeBo=jy6gL*rlfgQW^-R'(k`e-sX~@:k/0'ES2\n4 Observations: 2A: The purified crystals of sulfanilamide were in the shape of needles, white, and slightly translucent. This content was COPIED from BrainMass.com - View the original, and get the already-completed solution here! In the old fashioned process, we used buttermilk sugar and a bit of vanilla. Methyl alcohol has both polar and nonpolar parts so fluorene is not The dissolved material has a decreased solubility at lower temperatures and will separate from the solution as it is cooled. The, general technique involves dissolving the material to be crystallized in a hot solvent (or, solvent mixture) and cooling the solution slowly. Examples include: As a sulfonamide antibiotic, sulfanilamide functions by competitively inhibiting (that is, by acting as a substrate analogue) enzymatic reactions involving para-aminobenzoic acid (PABA). This increases the purity of the melt, so the melting temperature increases somewhat. >> vtnnktVjRU4;jmT[JYm6*V,6VB7A^(eFYfZQkj"Br~V+jQKWZkhTr0~JW,R)W*EP|KB1S,FP?g ?^5me#IOy~xyl.&3T&dt2_l,dszeTL's|"mCn#md` nsfA^MhFvNyI ZpC-M=M&FQ(*fp8/)6m^s-Hja;@LNXt?rm{