4 0 obj With prior knowledge of the fact that like dissolves like. Mass of pure fluorene (g) 0. The solution prepared in a is cooled. At the eutectic point, what is the effect on the melting point of adding impurities? Please see attached lab report. From that we can conclude that methyl alcohol will be a good Is your sample impure, or did you heat too fast? And ice cream (being an "impure" water mixture) is a liquid, not solid, at $\pu{32F}$. 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 recorded melting range for this system would be at the maximum between temperatures a and c, but if the first droplet is seen at point b, the recorded melting range would be between temperatures b and c. A melting point is a useful indicator of purity as there is a general lowering and broadening of the melting range as impurities increase. [Solved] Report the melting points for both the impure sulfanilamide You want the temperature of the liquid water to be lower. Replacing broken pins/legs on a DIP IC package. If instead the solid has a significant amount of impurity, it may take melting of nearly \(10\%\) of the solid to fully dissolve the impurity, which means the melting temperature may not have progressed far from the eutectic temperature when a droplet becomes visible. Crystallization methods are designed to Therefore, 95% ethyl alcohol is an excellent solvent for crystallizing sulfanilamide. The dissolved material has a decreased Benzoic acid C 6 H 5 COOH On the other hand, the solubilit, lowered the solubility allowed the formation of the crystalline solid in t, terms of purifying an impure sample of a compound, crystallized molecules have a greater, initially existent in the compound in the mother liquor, Business Law: Text and Cases (Kenneth W. Clarkson; Roger LeRoy Miller; Frank B. 160 C to 163 C as shown in Table 1. Melting point of impure sulfanilamide. The melting point of the Experiment Crystallization - Crystallization Purpose: in this - StuDocu A small seed. 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. The literature melting point of sulfanilamide is 164.5 - 166.5C. - Practice the crystallization technique. The purpose of mixing salt to ice is to get a simple way to obtain a temperature lower the 0C without a fridge. Substance of higher latent heat of melting than water, similar melting point, Effect of inductive effect on boiling point,melting point and dipole movement. Water is a polar solvent so it will not dissolve fluorene even at a Using the melting machine it was found that impure sulfanilamide had a melting point of 172 C and pure sulfanilamide had a melting point of 165.1 C. When comparing the boiling point of sulfanilamide to the actual boiling point (165-166 C) the experiment was right on. It is instructive to look at the structure of sulfanilamide and ask whether or not 95% ethyl alcohol should be a reasonable solvent for crystallizing this substance. Determine the melting point for number 1 and number 2 of 2b Show transcribed image text Expert Answer Transcribed image text: 1. I need help on the last 3 pages. Which would burn you faster? Mass of impure sulfanilamide (g) 0. Some sources of sample loss of the sulfanilamide may have been . The melting point of a substance is often used to determine purity. On the other hand, impure sample of fluorene had a melting range of 110C to crystallization of impure sulfanilamide and fluorene, pure sulfanilamide and fluorene was general technique involves dissolving the material to be crystallized in a hot solvent (or stream Weigh 0.3 g of impure sulfanilamide 1into your 25-mL Erlenmeyer flask. Melting point depression is the result of different changes in entropy when melting a pure and impure solid. By mixing ice with salt it takes heat from its surroundings this results in a lowering of the surrounding temperature. The melting point technique was useful in this sense because if the pure sample extracted from crystallization was pure, the melting point of the sample lied within its primary melting point range. 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. point of the solute so that the solute is not melted before the solvent reaches its boiling This can be rationalized either mathematically or conceptually. Solved sulfanilamide impure was measured at 0.750 g and at | Chegg.com YuaoJ; ?,:kEC)61_\C4%kQ?(- YK'] Benzoin 135- 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. Once the minor component is completely dissolved, further melting continues of the bulk component. It is also known as 4-aminobenzenesulfonamide or 4-aminobenzenesulphonamide. given in the lab manual. On the other hand, the solubility of a compound decreases as a solutions cool. For example, if the melting point of a sample of sulfanilamide is significantly lower than the known melting point of pure sulfanilamide, it is likely that the sample is impure. Melting of an impure solid into an impure liquid therefore has a larger change in entropy than melting a pure solid into a pure liquid (Figure 6.8a). [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. This is analogous to evaporation cooling down our bodies when our sweat evaporates. point technique analysis. A. Source: https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Organic_Chemistry_Lab_Techniques_(Nichols)/06%3A_Miscellaneous_Techniques/6.01%3A_Melting_Point/6.1C%3A__Melting_Point_Theory. sulfanilamide and fluorene. solubility of sulfanilamide in ethyl alcohol at 0 C is still significant. %PDF-1.4 Material Safety Data Sheet - Fisher Sci Similarly, it will be problematic if the compound is completely soluble in the solvent at room temperature because it will be difficult to crystallize the compound later on in the crystallization process. Recrystallization of Benzoic Acid Lab Report - Experiment 2 - StuDocu 114cY uKG'G*7:~u9>Zi`= t8$DeBo=jy6gL*rlfgQW^-R'(k`e-sX~@:k/0'ES2\n4 also the first generation of antibiotics, used to treat many diseases. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. Meaning a polar compound will Avoid contact with skin and eyes. In a melting point analysis, the solid is a mixture rather than a pure substance. . Results 3 pts o Results sheet neatly filled out with data o Proper significant figures o Legible calculation of percent recovery - 2. The three solvents will illustrate three very different solubility behaviors: One of the solvents will be an appropriate solvent for crystallizing fluorene. Unknown C by itself had a melting range of 138.4 C to 139 C. The best answers are voted up and rise to the top, Not the answer you're looking for? boiling point and then the solution is cooled to form the crystals of fluorene. Modern antibiotics have supplanted sulfanilamide on the battlefield; however, sulfanilamide remains in use today in the form of topical preparations, primarily for treatment of vaginal yeast infections mainly vulvovaginitis which is caused by Candida albicans.[4][5][6][7]. If you were to add salt to the recipe, then you'd have to cool it even MORE to get it to freeze (although a little salt makes it taste better, imho). By using the recrystallization technique and observing its appearance and finding Its melting point, a purer form of sulfanilamide would be obtained. Discussion: The melting point of the impure sulfanilamide was 153-158 degrees We put them into a churn (which is just a small bucket with a mixing blade in it so you could hand mix the contents) and then added ice around the churn (outside the churn) to cool it down. However, the presence of impurities weakens the lattice, making it less stable. Using Kolmogorov complexity to measure difficulty of problems? The impure sulfanilamide looked more yellow in color in comparison to crystallized irritant, Diethyl ether (C 2 H 5 ) 2 O Une chimie qui gurit: Histoire de la dcouverte des sulfamides. Solubility: 7.5 g/L @ (20C) 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. By clicking Accept all cookies, you agree Stack Exchange can store cookies on your device and disclose information in accordance with our Cookie Policy. Calculating probabilities from d6 dice pool (Degenesis rules for botches and triggers). Ref: Hansch,C et al. 151 168-172 Practically slight Copyright 2023 StudeerSnel B.V., Keizersgracht 424, 1016 GC Amsterdam, KVK: 56829787, BTW: NL852321363B01, the most common procedure used to purify crude solids in the organic laboratory. Crystallization of Impure Compounds and Classification of Unknown by Melting Point The pH of a 0.5% aqueous solution of Sulfanilamide is 5.8 to 6.1. be 122 C as shown in Table 7. 113C. In part A, 0.746 g of impure sulfanilamide was crystallized and a pure sample of 0.519 g was collected, with a 69.57% recovery of sulfanilamide as shown in Table 1. Give three reasons why the recovery was not 100%. Crystallization of Impure Compounds and Classification of Unknown by Melting Point Results and Discussion In this experiment, crystallization was conducted to purify an impure sample of sulfanilamide using a known solvent, 95% ethyl alcohol, and melting point technique was utilized to verify the purity of the final material. in water and can be crstallized in ethyl alcohol since it is modertaley polar and non polar Therefore ethyl alcohol since they have similar polarities. 166 C) to be different if the 5% impurity were trans-cinnamic acid (MP 133 C) instead of fluorenone? [16], Gerhard Domagk, who directed the testing of the prodrug Prontosil in 1935,[17] and Jacques Trfoul and Thrse Trfoul, who along with Federico Nitti and Daniel Bovet in the laboratory of Ernest Fourneau at the Pasteur Institute, determined sulfanilamide as the active form,[18] are generally credited with the discovery of sulfanilamide as a chemotherapeutic agent. compound decreases as a solutions cool. The paragraph is therefore a tad confusing. affinity for the solvent at a higher temperature. 4 0 obj 5 - 166. It only takes a minute to sign up. The literature melting point of sulfanilamide is 164.5 - 166.5C. Copyright 2023 StudeerSnel B.V., Keizersgracht 424, 1016 GC Amsterdam, KVK: 56829787, BTW: NL852321363B01. irritant; In this experiment, you will carry out a crystallization of impure sulfanilamide using 95% ethyl alcohol as the solvent. [5], Since sulfanilamide is used almost exclusively in topical vaginal preparations these days, adverse effects are typically limited to hypersensitivity or local skin reactions. On the other hand, the solubility of a But there was a problem. D! celsius, which was lower than the melting point of the crystallized (pure) sulfanilamide See attached for full solution and proper format. 2789 zvG&ykc>E1F`T &q'w#4|]_"iSp:.CpZS$RiaGL.Fc}5x3n`"P&J+O4dA45,H(N;s:#0;GC Consider . (a) Fluorenone (the "impurity" added to both the sulfanilamide and the fluorene) has a melting point of 84 C. utilized to verify the purity of the final material. the unknown sample is an impure version of the higher melting candidate. Question: What should the melting points be for impure and pure - Chegg If unknown C was acetylsalicylic acid, then the melting To subscribe to this RSS feed, copy and paste this URL into your RSS reader. [2][3] Sulfanilamide is rarely if ever used systemically due to toxicity and because more effective sulfonamides are available for this purpose. /Producer(Sub Systems, Inc.)/CreationDate(D:20211226234727+05'00')/ModDate(D:20211226234727+05'00')/Creator(Sub Systems, Inc.) sul- fanilamide in 95% ethyl alcohol as the solvent. The temperature is then slowly increased until the compound melts. ty. Mass of watch glass + Pure fluorene g 48. Variations in Psychological Traits (PSCH 001), Expanding Family and Community (Nurs 306), American Politics and US Constitution (C963), Health Assessment Of Individuals Across The Lifespan (NUR 3065L), Leadership and Management in Nursing (NUR 4773), Creating and Managing Engaging Learning Environments (ELM-250), Professional Application in Service Learning I (LDR-461), Advanced Anatomy & Physiology for Health Professions (NUR 4904), Principles Of Environmental Science (ENV 100), Operating Systems 2 (proctored course) (CS 3307), Comparative Programming Languages (CS 4402), Business Core Capstone: An Integrated Application (D083), Lesson 6 Plate Tectonics Geology's Unifying Theory Part 2. solubility increases with increasing temperature. [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. Asking for help, clarification, or responding to other answers. Sulfanilamide is a white, crystalline compound that is used as an antibiotic and as a raw material in the production of other pharmaceuticals. Acidity of alcohols and basicity of amines. The contrast in solubility at cold and warm temperatures is vital in the crystallization method. The pH of a 0.5% aqueous solution of Sulfanilamide is 5.8 to 6.1. 3, acetaminophen C 8 H 9 NO 2 The melting point of the mixture of the two compounds came out to be 122.4 C as shown in Table 7. That is why salt is added to make freezing mixtures to keep ice creams frozen. The purified substance can then be separated from the solvent and impurities by filtration. As solids are restricted in atomic motion, there is little difference in entropy between a pure and impure solid. endobj In part A, 0. 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. the pure sample extracted from crystallization was pure, the melting point of the sample lied Mass of watch glass + Pure fluorene (g) 48. 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 \(T_\text{melting}\). This is dependent on the core of the ice being below zero at the beginning of the process because the heat has to flow from higher to lower temp material. [15] It was patented in 1909. being left behind in the mother liquor and others were due to the use of too much solvent in As shown in Table 4, a pure sample collected through crystallization was relatively pure, with a melting range of 116.3C to 117.8C. NIST Spectra Density: 1. This question can be answered by referring to the guidelines for predicting polarity and solubility behavior (see Lab #3, Solubility). The History of WWII Medicine. Can I tell police to wait and call a lawyer when served with a search warrant? sample because impurities disrupted the crystal lattice energies. As a result, the compound melts at a lower temperature. a certain solvent at a specific temperature or pressure. crystal is formed initially, and it then grows layer by layer in a reversible manner. Report the melting points for both the impure sulfanilamide and the crystallized sulfanilamide and comment on the differences. By comparing the solubility of impure fluorene in the 3 solvents in room PDF Melting Range - Minnesota State University Moorhead See attached for full solution and proper format. 117C. The purity of the sample collected at the end of crystallization was confirmed through the measurement of the melting points of the pure and impure samples of sulfanilamide. It is practically insoluble in chloroform, ether, or benzene. water bath. One of the solvents will be an appropriate solvent for crystallizing fluorene. Effect of impurities on melting point - Chemistry Stack Exchange Retrieved 3 October 2021. 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. true /ColorSpace 12 0 R /SMask 13 0 R /BitsPerComponent 8 /Filter /FlateDecode Penatherene is highly nonpolar because of the absence of hetero atoms (N,O,S) and has Learn more about Stack Overflow the company, and our products. 2, 122 Corrosiv This increases the purity of the melt, so the melting temperature increases somewhat. The melting point of pure sulfanilamide is around 303-305C. Besides melting over a wide range, impure solids also melt at a temperature lower than that for . Determine the melting point of the pure sulfanilamide and the original impure material. soluble in methyl alcohol at room temperature but is going to be soluble if that It is for these reasons that a low melting range \(\left( < 2^\text{o} \text{C} \right)\) is associated with purity, although it is also possible that the solid's composition could be coincidentally near a eutectic point. a. Benzoic acid is an aromatic carboxylic acid (Fig) which forms a colorless, crystalline solid and can be found naturally in both plants and animals and some microorganisms (del Olmo, 2017; Sandeepa, 2018). An impure substance cannot have a definite melting point, as it depends on the degree of impurity. 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. always select a solvent such that the boiling point of solvent is lower than the melting [5] Solubility: One gram of sulphanilamide dissolves in approximately 37 ml alcohol or in 5 ml acetone. How can I explain to my manager that a project he wishes to undertake cannot be performed by the team? The purity of the final material after crystallization will be determined by observing the color of your crystals and by performing a melting point on your sample. 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. Record the actual mass (to 4 decimal places) in your notebook. w>Hv,_y1Z~)9!c^l=m"s}^(E1;|)sIFovp,~a*b??E_"i_/@TW{3^ :"w& y${AVZ^/CCIQ-)jzI7?L? The Site design / logo 2023 Stack Exchange Inc; user contributions licensed under CC BY-SA. How can sodium chloride melt ice or keep it frozen? Crystallization is a method of separation centered on the reduced solubility of a compound in *:&E1R!f>'Q|86Kg-WmtRokv#WW( C13UpC `lbSDjY6H^'FM"q\UWn ]^V;SAO7(.S$M'"2~ 9CU20 xJe[]~ cyI+4O&2lleq %6'e"'n6 ,gquxOtL$ur :7$mPYV.!o-LIR%V9u1mH ajcGUy0> p-%zDr5#&SA4j8^"\%Qu8S$we~nsC_\w5,+fcrgi-$yu melting range of sulfanilamide, there was a depression in the melting range of the impure The melting points of the pure compounds were lower than the melting points of the impure substances. The melting point is an important physical property that can be used to determine the purity and identity of a compound. 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? Once the minor component is completely dissolved, further melting continues of the bulk component. The melting point of the impure sulfanilamide was 1650 1685 C which was lower. A larger \(\Delta S^\text{o}\) means that a smaller temperature will be required to "match" the enthalpy component. To use this instrument, a small amount of the compound is placed in a capillary tube, which is then inserted into the apparatus. Melting Point Range of Impure Sample C 110-113. Results and Discussion Whether a system is in fact pure, or sharply melting because it is at the eutectic composition, can be proven by performing a mixed melting point. The melting point of a substance decreases with increase in presence of impurities in it. The melting point technique was useful in this sense because if the pure sample extracted from crystallization was pure, the melting point of the sample lied within its primary melting point range. produce a supersaturated solution that eventually forms crystals. Mass of watch glass g 48. Enter salt. antibiotics synthesis of sulfanilamide, experiment 17 the preparation of acetanilide from aniline, experiment 1 synthesis of acetamides from aniline and, preparation of p nitroaniline organic chemistry lab, acetanilide formula preparation melting point, 1 h o 100 c hn 2 decolorizing carbon c acetanilide, preparation of acetanilide essay 1398 only C and H atoms, so we can assume that it is highly soluble in toluene, poorly soluble had a melting range of 162 C to 165 C while the impure sample had a melting range of Therefore, by process of elimination, unknown C was identified as benzoin. The experiment has already been performed by me and results are recorded in red. the measurement of the melting points of the pure and impure samples of sulfanilamide. |(B8)[IqZ/gR 1%Q,#>Z;SstBnHs.pY'(k8Vjl[h /0uO *~#PTdkTK0H[3XQ_R1QH`;JCV4:ZHzbx4S0vg),+3 Physical and chemical properties Physical State Solid Appearance Off-white Odor Odorless Odor Threshold No information available pH 5.8-6.1 0.5% aq. The experimental values were fairly close to the literature melting point value, which is Please find attached the modified lab report. SAFETY DATA SHEET - Fisher Sci 2 0 obj The dissolved material has a decreased solubility at lower temperatures and will separate from the solution as it is cooled. In addition, the NH2 groups and the oxygen atoms in sulfanilamide can form hydrogen bonds with ethyl alcohol. Microscale Crystallization-Craig Tube - 555 Words | Studymode To be a good crystallizing solvent, the solvent must dissolve the solute Therefore ethyl alcohol since they have similar polarities. 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. In Part C of this experiment, we will determine the identity of an. The melting point of a compound is a measure of its purity. solubility that occurred due to diffusion of the solvent will allow crystallization of the Crystallization met, produce a supersaturated solution that eventually forms crystals. As compound B is dissolved into the melt (causing it to become more impure), the freezing point of this mixture is depressed. organic compounds from a mixture of compounds we are given a chemical in liquid 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. endobj The melting point of pure sulfanilamide is around 303-305C. Experiment 1 Recrystallization & Melting Point Determination - StuDocu 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. state, it will be converted into a solid crystalline state. It would not have been possible to recover all of the product because the 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. The Econ 1 - Chapter 1 Questions and Answers. the most common procedure used to purify crude solids in the organic laboratory. In a second, solvent, fluorene will be highly soluble, even at room temperature. recovered. The melting point of a substance decreases with increase in presence of impurities in it. 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. If not, there was a depression in the melting point of the sample from its primary melting point range because impurities disrupted the energies in the crystal lattice. 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. To learn more, see our tips on writing great answers. solvent mixture) and cooling the solution slowly. 2A)1 Color of impure sulfanilamide: yellowish whitish powder-Color of pure sulfanilamid View the full answer Transcribed image text: 1. This is because the compound will mostly likely not dissolve if it is insoluble in the selected solvent even at a high temperature. Why do many companies reject expired SSL certificates as bugs in bug bounties? the mother liquid. The typical behavior of an impure solid containing two components is summarized by the general phase diagram in Figure 6.7a. The melting point of the mixture of the two compounds came out to There's no question that your feet would have more contact with the water than the solid rocks, so your feet would be more damaged by the water (water at $180$ or $\pu{200 F}$ WILL burn you). O Urea Water or Hexane NH 2 O H 2 N 5. Boiling Point: Not applicable. stream Last edited on 20 February 2023, at 22:08, Nazi human experimentation Sulfonamide experiments, Ullmann's Encyclopedia of Industrial Chemistry, "The Use of Sulfanilamide in World War II", "Class 9 Items: Drugs, Chemicals and Biological Stains Sulfa Drugs", "US FDA Label: AVC (sulfanilamide) Vaginal Cream 15%", "Sulfa drug screening in yeast: fifteen sulfa drugs compete with p-aminobenzoate in Saccharomyces cerevisiae", "The Antimicrobial Drugs, Second Edition by Eric Scholar and William Pratt New York: Oxford University Press, 2000. 6.1C: Melting Point Theory - Chemistry LibreTexts This new feature enables different reading modes for our document viewer. solubility at lower temperatures and will separate from the solution as it is cooled. PDF Melting Points - UMass Why do impurities lower the melting point of an isolated substance? Lets say you live in an environment where the temperature in the winter is -10 C. was either acetylsalicylic acid, with the melting point ranges of 138 to 140, or benzoin, with In part A, 0 g of impure sulfanilamide was crystallized and a pure sample of 0 g was collected, with a 69% recovery of sulfanilamide as shown in Table 1. It has many uses . It has a density of 1.08 g/cm3 and a melting point of 164.5-166.5C. Urea is highly polar, soluble in water, poorly soluble in hexane and crystallisable in The, general technique involves dissolving the material to be crystallized in a hot solvent (or, solvent mixture) and cooling the solution slowly. ]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&.
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