Experiment. 8 Materials required Equipment and special glassware Time required : Key references Estimation of phosphoric acid in cola drinks by molybdenum blue method Coca-Cola / Pepsi cola / Thums up KH,PO, Cone. sulfuric acid Dilute sulfuric acid Ammonium molybdate (NH,),Mo,O,, Ascorbic acid Standard flasks (1000, 250 and 100 ml capacities) Water bath UV-visible spectrophotometer and accessories 3 hours 1, Lozano-Calero, D.; Martin-Palomeque, P.; Maduefio- Lorguillo, S., J. Chem. Educ., 73, 1172, 1996. 2. Murphy, J., J. Chem. Educ., 60, 420, 1983.48 A collection of interesting general chemistry experiments PRINCIPLES Among the various ingredients of cola drinks, one which is rather odd and worrying to many, is phosphoric acid. Phosphoric acid is well-known to many as a rust remover and its salts as additives in detergents and as fertilizers. In the steel industry, it is used for providing —rust-proofing, a method known as parketing. A combination of phosphoric acid and manganese dioxide are the main ingredients for parketing which works as an excellent tust-free ~ pre-treatment — for military equipments made of carbon steel. In addition, car bodies, refrigerators, washing machines and many electrical gadgets with painted or enameled surfaces also use phosphatized undercoats to prevent the paint from blistering and peeling. In food materials such as colas, beer, jams, jellies and cheeses, The recipes of the two well-known soft drinks, Coca- Cola (John Pemberton; 1886) and Pepsi cola (Caleb. D. Bradham ~1890) are a matter of immense curiosity to many, The common major ingredients in both the drinks are sugar, caramel, caffeine, phosphoric acid, and lime juice. The flavoring agents vary. The Coca cola flavoring formula, known as the 7x, has been made public in 1993 in a book called “For God, Country and Coca-Cola” as oils of lemon (120 parts), orange (80), nutmeg (40), cinnamon (40), neroli (40) and coriander (20). Pepsi cola had disclosed their composition when it went bankrupt in 1923, Their flavoring formula has five ingredients common to that of Coca-Cola. Since the initial years, the composition has changed for both the soft drinks. Cocaine and glycerin that were originally there in Coca-Cola and pepsin (a digestive enzyme from which the name Pepsi came) that was present in Pepsi has been removed. Pepsi on the internet, admits that their products do have some minute alcohol content used for dissolving their flavoring agents but Coca-Cola declines having any phosphoric acid provides a tart, acidic flavor. Living organisms require phosphates to make DNA, ATP and bones (calcium phosphate). Sodium tripolyphosphate, an important ingredient (up to even a third of its weight) in phosphate detergents, soften water by complexing with calcium and magnesium. In the 1980s, use of phosphate detergents alcohol in its composition. Coca-Cola initially had only citric acid, which was later changed to phosphoric acid. was opposed by environmental groups as it was ° Q sini sfcati ; HO. \, OH claimed that they lead to eutropification of lakes, and Sp SoH many companies replaced phosphates by zeolites in Ho 5 detergents. However, in the late 1990s, further studies e (e.g. The phosphate report, by Bryn Jones, former os pcoH director of the Green Peace organization) indicate that on “OH the overall effect on the environment is similar for oP both zeolites and phosphates. Trisodium phosphate has recently been found to be useful in the removal of ° a HO, 7 food poisoning germs such as salmonella from raw 1 SR meat. The bacteria are eliminated by spraying HO” On, 0H trisodium phosphate which removes the surface fat o/ You layer of the meat on which micro-organisms thrive. Plants extract phosphates from soil and they also store phosphates as a chemical, phytic acid in their Phytic acid: The phosphate-rich molecule present in seedsExpt. 8 Estimation of phosphoric acid in cola drinks by molybdenum blue method 49 seeds, so that when the seeds germinate, they can put down roots without needing to take in any phosphates from the environment. In total contrast to phosphoric acid and phosphates, many organophosphorus compounds, where one has one or more alkyV/aryl groups bound directly to the phosphorus, are highly poisonous, Many are well-known as organophosphorus pesticides and even notorious as nerve gases such as Sarin and Tabun. The commercial method of preparation of phosphoric acid is by the addition of sulfuric acid to phosphate rock. Pure anhydrous phosphoric acid is a white solid that melts at 42 °C to form a viscous liquid. In solution, phosphoric acid behaves as a triprotic acid, having three ionizable hydrogen atoms. The hydrogen ions are lost sequentially. H,PO,(aq) === H'(aq) + H,PO,(aq) K, =75 x10 H,PO,(aq) === H'(aq) + HPO?“(aq) K,,=6.2x 10° HPO? *(aq) === H'(aq) + PO,*(aq) K,,=17x 102 Product Phosphate ingredients Function of phosphate Antifreeze Dipotassium phosphate Buffer that controls pH Superphosphates Ca(H,PO,),. H,O Fertilizer Athletic drink Monopotassium phosphate Potassium source to help prevent muscles from cramping Washing detergent Sodium tripolyphosphate Softens water, suspends soil, Chicken (processed) Baking powder Car wash detergents Cola drinks Laxatives Evaporated milk Frozen fish French fries Gelatin and common salt Fire extinguishers Instant pudding Processed cheese Pet food Tooth paste Cake mixes Sodium tripolyphosphate Monocalcium phosphate/Sodium acid pyrophosphate Sodium tripolyphosphate Phosphoric acid Sodium dihydrogen phosphate Disodium phosphate dihydrates Sodium tripolyphosphate/Sodium hexametaphosphate Sodium acid pyrophosphate Tricaleium phosphate Monoammonium /Diammonium phosphate Tetrasodium pyrophosphate/ Disodium phosphate anhydrous Disodium phosphate dihydrate Sodium tripolyphosphate Sodium monofluorophosphate/ Dicalcium phosphate dihydrate Sodium aluminum phosphate Promotes protein/water binding and removes salmonella bacteria Leavening agent that helps baked goods rise Softens water, removes soil, and keeps soil from redepositing Enhances flavor and tartness With NaHCO, brings about effervescence Maintains suspension of milk proteins Inhibits moisture loss on thawing and retains the natural flavor Prevents darkening of potatoes Prevents clumping when liquid is added to the powdered granules Fire retardant Thickening agent Controls texture and promotes uniform melting Promotes protein/water binding Fluoride source in toothpaste and abrasive to help clean teeth Leavening agent that helps baked goods rise50 A collection of interesting general chemistry experiments Phosphoric acid is not a particularly strong acid as indicated by its first dissociation constant. It is a stronger acid than acetic acid but weaker than sulfuric acid and hydrochloric acid. Each successive dissociation step occurs with decreasing ease. Thus, the ion H,PO,” is a very weak acid and HPO,?” is an extremely weak acid. Replacing one, two, or three of the hydrogen ions can form salts of phosphoric acid. For example, NaH,PO,, sodium dihydrogen phosphate, can be formed by reacting one mole of phosphoric acid with one mole of sodium hydroxide. Similarly, Na,HPO,, disodium hydrogen phosphate, and Na,PO,, trisodium phosphate, can be formed by the reaction of one mole of H,PO, with two and three moles of NaOH, respectively. Some of the important uses of phosphates in daily life are given in previous page. It needs to be mentioned that phosphoric acid in colas and phosphates in food presents no threat to health (although it has been accused of inducing tooth decay and weak bones) and that the human body uses phosphoric acid and phosphates for a variety of functions. Excess phosphate is continually removed as Na(NH,)HPO, by the kidneys. The alchemist, Hennig Brandt isolated the element phosphorus for the first time in 1669 from urine, carbon and sand. Isopoly and heteropoly acids and anions of molybdenum An important feature of the chemistry of oxides of tungsten and molybdenum is the formation of numerous polyoxomolybdate(VI) and polyoxotungstate(VI) acids and their salts. When trioxides of molybdenum and tungsten are dissolved in strong aqueous alkali, they form normal molybdates and tungstates such as Na,MoO, having tetrahedral anions. Under strongly acidic conditions these solutions give the yellow molybdic acid MoO,,2H,0 or the white tungstic acid WO,.2H,O. At pHs between these two extremes, polymerization or aggregation occurs leading to what are known as isopolyanions, which are almost invariably made of the MoO, octahedra. For example, under such conditions ammonium molybdate forms the stable ammonium paramolybdate (NH,),Mo,0,,.4H,9, also known as ammonium heptamolybdate. In 1826, J.J. Berzelius found that acidification of solutions containing both molybdate and phosphate produced a bright yellow precipitate. This was the first example of a heteropolyanion and it actually contained the phosphomolybdate [PMo,,0,,]*. Since its discovery, a host of heteropolyoxometallates have been prepared, mostly with molybdenum and tungsten, with more than SO different heteroatoms. The phosphomolybdate [PMo,,O,,}*, itself can be used for quantitative estimation of phosphates and the phosphotungstic acid is an excellent acid catalyst. The structure of this anion is known as the Keggin structure, named after the person who first determined it. It can be best described as having a tetrahedral phosphate, surrounded by 12 octahedral MoO, units, each sharing one or two oxygens between themselves. The MoO, units can be envisaged to form four clusters having three units each, and these clusters are tetrahedrally placed around the phosphate, bound through its oxygens. 7 H,PO, + 12 (NH,),Mo,0,,.4H,0 — 7 (NH,),{PO,(MoO,),,] + 51 NH,OH + 33 H,OExpt. 8: Estimation of phosphoric acid in cola drinks by molybdenum blue method 51 One of the interesting reactions of heteropolymolybdates and tungstates is their mild and reversible reduction, which result in intense and characteristic blue colors (heteropoly blues). The reductions are mostly of two electron equivalents but can be of one and up to six electron equivalents. Quite interestingly, during this reduction, there is no structural change and the heteroatom, even if it is a metal, is not involved. In the case of (NH,),PMo,,0,,, the partially formed Mo(V) transfer its electrons to Mo(VI) resulting in the intense blue color and a characteristic absorption band at 830 nm. This reduction and measurement of the intensity of the blue color by UV-visible spectroscopy forms the basis of the colorimetric estimation of phosphoric acid in this experiment. In the experiment, the hexavalent molybdenum phosphate is reduced to the blue, partially pentavalent form by ascorbic acid. The intensity of the blue color is measured spectrophotometrically at 830 nm. PRocEDURE In the absence of deionized water, distilled water can be used. 1, Weigh 1.94 g of dry KH,PO,, (AR grade) and dissolve in deionized/doubly distilled water in a 1 | volumetric flask. Make up the solution (the phosphorus content of this solution expressed as P.O, is 1000 ppm). (solution A) 2. From the solution A, pipette out 5 ml into a 100 ml standard flask and make up. (solution B) 3. From solution B, pipette out 8 ml into-a 100 ml standard flask and make up to the mark. This solution C will be the working standard solution and will have 4 ppm of P,0,. 1. Dissolve 1.00 g of ammonium paramolybdate in 50 ml of deionized water and 1.76 g of ascorbic acid in 100 ml of deionized water. Dilute 17 i of concentated sulfuric acid in 200 ml of deionized water F 2. Place 39 ml of ammonium molybdate solution, 60 ml of the ascorbic acid solution and 125 ml of dilute sulfuric acid into a 250 ml standard flask. Make up the solution. 3. To eliminate gases from the cola, it should be transferred to a beaker, the level marked with a pen and gently boiled for few minutes making sure that the level of the solution does not decrease. The cola can also be kept open at atmospheric pressure for 24 hours before analysis. 4. Pipette out 5 ml of the cola into a 100 ml volumetric flask and make up with deionized water. 5. Make solutions as shown in the table in 20 ml test tubes. Warm the test tubes for 30 minutes in a water bath of 50°C. Measure the absorbance against a blank at 830 nm. Make at least 3 measurements of the unknown sample.52 A collection of interesting general chemistry experiments 6. Plot absorbance versus concentration of the standard solution. From the graph, determine the concentration of the unknown cola sample. Calibration curve Sample Volume of working standard solution (ml) 0 1 2 #3 4 5 Volume of diluted cola sample (ml) 05 Reducing solution (ml) eee me ge Deionized water (ml) Geog eoeere pra ieeeeeaea| Final volume (ml) 10 10 10 10 10 10 10 Concentration as P,0, (ppm) 0 04 08 12 16 2