CHE130L Analytical Chemistry Laboratory I. OBJECTIVES II.

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON

Upon completion of the experiment, the student should be able to: Define the principles and proper techniques involved in precipitation and gravimetric analysis perform properly the relevant techniques in precipitation and gravimetric analysis; i.e. washing, ignition and digestion; and, calculate the amount of iron in an unknown sample using gravimetry.

LABORATORY EQUIPMENT / INSTRUMENTS / REAGENTS Equipment/Apparatus Crucible and cover Glass funnel Wire triangle Glass rod Rubber policeman Dessicator 250 mL beaker 400 mL beaker Tongs/test tube holder Iron ring Clamps Hot hands Heating pad Bunsen burner Analytical balance Quantity 2 1 1 1 1 1 2 2 1 1 1 1 1 1 1

Chemical/ Reagents/ Materials 3M HCl (corrosive) Litmus paper 6M HNO3 (corrosive, oxidizing agent) 3M NH3 (corrosive) 12M HCl (corrosive, releases fumes) Filter paper (regular & ashless) Unknown sample with iron Distilled water in wash bottle

Experiment 6: Gravimetric Determination of Iron

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CHE130L Analytical Chemistry Laboratory III. Introduction Discussion

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON DISCUSSION OF FUNDAMENTALS

Analytic chemistry is concerned with the critical measurements of anything that involves chemicals and substances and such, quantitatively or qualitatively. One of the methods acquainted with analytical chemistry would be classical methods, which involves the various measures of solidstate substances. Under this classification would be one of the most important aspects of analytic chemistry, which is gravimetry, which is the simplified counterpart of stoichiometry. Stoichiometry is the relation between quantities of substances that take part in a reaction or form a compound (typically a ratio of whole integers). Using stoichiometric relations is not hard typically if you understand how it moves around back and forth, but writing it down includes some length of time. Alas, gravimetry is born. To make up for this kind of lengthy solving, gravimetry only uses a single ratio that converts one another but still follows Daltons law of mass and proportions, which is called the gravimetric factor. GF is used to convert substances that are specifically related to one another, which is a principle of mass conservation. Though in a way, gravimetry is limited in such a way that the experimental process of determining the values should be undergoing a gravimetric analysis. It includes preparing the solution, precipitating, digesting, filtering, weighing and drying/ignition. This experiment will focus on the gravimetric determination of iron, from an unknown compound with an iron composition. Gravimetric analysis steps will be used, as the unknown compound will be prepared to precipitate to gelatinous rust ( ). It is ignited to lose the water on it, forming rust. Continuous constant weighing will in the end get the percentage iron of the sample.

Gravimetric analysis is an analytical method which uses mass measurements and knowledge of reaction stoichiometry to determine the amount of analyte/s in a sample. Such procedures are exemplified in the gravimetric determination of iron. The analysis is based on the fact that iron as Fe3+ species forms an insoluble precipitate as iron (III) hydroxide. The formation of this precipitate is pH dependent (above pH 5), and the precipitates in a mixture include iron (III) hydroxide, Fe (OH)3 and FeO(OH), usually represented as Fe2O3xH2O. The latter is a gelatinous precipitate which contains appreciable amount of water that makes quantitative determination of iron difficult. In such a case, the iron should be completely precipitated in a form that is useful for gravimetric analysis.

Experiment 6: Gravimetric Determination of Iron

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CHE130L Analytical Chemistry Laboratory Application

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON The first part should ensure that iron in a sample mixture is converted to Fe3+ form (Hage and Carr 2011). The samples can be heated with a mild oxidizing agent such as bromine water or nitric acid to convert Fe2+ to Fe3+. The pH is controlled by precipitating the iron in ammonia instead of NaOH. The use of ammonia not only controls the pH of the solution but also prevents coprecipitation of any other insoluble metallic ions into metal hydroxides. Since ammonia is highly volatile, it can be easily removed from the final sample such that the sample is free from impurities. After precipitation, the sample undergoes filtration, dissolution of the precipitate with HCl to lower the pH, and a second precipitation step by addition of fresh ammonia. This second precipitation step helps to further lower the amount of metal ions aside from Fe3+ to precipitate. This final precipitate is then washed several times with ammonium nitrate until the gelatinous iron (III) hydroxide is formed. Ignition is then done to convert the hydroxide into a well-defined form of iron, iron (III) oxide, Fe2O3.

Gravimetry has many practical applications, and from what we are discussing in the lecture, gravimetry involves the conversion of a compound to another compound that is related by their molecular formulas, i.e. both have arsenic, though one is a sulphate whereas one is a nitrate. Gravimetric analysis provides information as to the determination of percentages of metallic substances in a sample, as to which the sample contains any compound that is molecularly related to the metal in query.

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CHE130L Analytical Chemistry Laboratory IV. METHODOLOGY About 0.60 g of the sample was weighed into a 400-mL beaker. 15-mL water and 10mL of 3M HCl. 5-mL of 6M HNO3 was added. It was then boiled until it was clear yellow. The sample was diluted to 200-mL with distilled water. 3M ammonia was added with constant stirring until the solution was basic. The precipitate was digested by boiling.

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON

The crucible was heated until it started to glow orange.

After heating, the set up was let to cool in the open for 20-30 minutes.

The steps were repeated until constant weigh was observed.

After the crucible has been cooled, it was then placed in the desiccator and was weighed in the analytical balance.

Figure 1. Constant mass of the crucible

The filtration set up was assembled while waiting for the precipitate to settle. The supernatant liquid was decanted through the filter paper.

When ignition was completed, the crucible was let to cool in the open and was transferred to the desiccator.

The filter paper was allowed to drain thoroughly.

The precipitate and crucible were weighed and the steps were repeated until constant weight was seen.

The filter paper containing the precipitate was heated while inside the crucible previously heated to constant mass.

Weight percent of iron was calculated in every sample. Average and average deviation were also reported.

Figure 2. Gravimetric determination of iron

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CHE130L Analytical Chemistry Laboratory V.

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON DESCRIPTION OF THE APPARATUS / SET - UP

Figure 1. Ignition Set-up

The ignition set-up is done to primarily dry the washed filtrate, which is usually in its gelatinous form. This is very important to do, especially since we didnt know how much hydrate molecules have been stuck up in the precipitate, so in all doing getting the pure precipitate will lead you to more accurate results as pertained to the gravimetric determination of a certain substance.

Experiment 6: Gravimetric Determination of Iron

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CHE130L Analytical Chemistry Laboratory VI. DATA SHEET

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON

Table 1. Constant weight of Crucible Trial 1 2 Mass (g) 42.241 42.241

Table 2. Weight of unknown sample Weight of unknown iron sample (g) 0.598

Table 3. Constant weight of Crucible + Sample Trial 1 2 3 Ave Weight 0.1761 Iron Mass (g) 42.4266 42.4173 42.4171 42.4172

Experiment 6: Gravimetric Determination of Iron

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CHE130L Analytical Chemistry Laboratory VII. SAMPLE CALCULATIONS VIII. RESULTS AND DISCUSSIONS

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON Table 4. Percentage iron Trial 2 3 Average % Iron 20.58 % 20.61 % 20.60%

The experiment is all about the gravimetric determination of iron. Gravimetric analyses rely on some final determination of weight as to getting on quantifying an analyte. Since weight can be measured better and more precisely than any other state, since liquids are always measured by their volume, and their measuring instruments prove to be quite estimate-friendly, which proves it to be systematic error related. And another, it is the most accurate to be measured among any other fundamental properties. With this, gravimetric analysis is one of the most accurate classes of analytical methods available. This branch of the classical method amongst analytical chemistry is one of oldest techniques, and proved to be very important. The experimental process may be quite lengthy and tedious, since samples are extensively treated to remove interfering substances (or the matrix). As a result, gravimetric methods in experiments are not popularly used amongst environmental analysis (i.e. petroleum gathering in the depths of the Earth, etc.).

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CHE130L Analytical Chemistry Laboratory

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON The gravimetric analysis process is subdivided among four different types; physical gravimetry, electrodeposition, precipitate gravimetric analysis and thermogravimetry. The differences between these types is on the acquisition of the sample before weighing the analyte, or in simple terms, how to prepare it. Physical gravimetry is the one that is commonly used in environmental engineering. It involves the physical separation and classification of the matter that is found in the samples in the environment, from which the separation and classification would be differed on their particle size (i.e. total suspended solids or colloids) and its volatility (evaporating readily at normal temperatures in pressures, for liquids or for those who behave like liquids i.e. Non-Newtonian fluids). Electrodeposition is the electrochemical reduction of a cation (a metal ion, to be specific) at a cathode, and the simultaneous deposition of the ions on the cathode itself. Precipiate gravimetric analysis is pretty self explanatory, as it acquires its analyte from precipitating it from a sample through a series of chemical reactions. Since this is the easiest methods amongst all four, this proved to be a great method in the environmental field, specifically pertaining to sulfite (since sulfite is generally insoluble to any other ion you will mix it with, citing a few exceptions, for most). Lastly, thermogravimetric analysis samples with hydrates or something that can be evaporated is heated, and the changes in mass are also recorded. Volatile solids are of major concern to this type of gravimetric analysis. In this experiment, we are going to gravimetrically determine the percentage of iron through an unknown iron sample, which the combined process of thermogravimetric and precipitate gravimetric analysis. The experiment started with the determination of the constant weight of the crucible. The crucible is to be heated strongly with a Bunsen burner as shown. This process is done since all solids have a certain affinity to water, even the containers. If exposed in the air, even under laboratory conditions, it might pick up water molecules from vapor, adding weight to the object. Also, water is a viable medium Figure 3. Heating set-up. to grow bacteria, which can also contribute to the mass of the object. With this, the subject must be either heated or be put in a dessicator. The crucible is then heated to become orange. To further ensure that the heat is evenly spread among the crucible, the clay triangle that supports the crucible should be glowing. This can be done in a faster way when the crucible is placed in the hottest position of the flame, in this flames case, the light blue portion inside. This process is continued for ten minutes, letting the heat in and out to avoid cracking of the crucible (since it cannot sustain that much heat at a prolonged period of time). After heating, it will be cooled by putting it in a rubber mat with aluminum sheets, to room temperature. The crucible Experiment 6: Gravimetric Determination of Iron 8|Page

CHE130L Analytical Chemistry Laboratory

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON can be cooled in the triangle after heating, however, the heat that the triangle received can be transferred to the crucible. Moreover, the aluminum in the mat provides conduction of the heat from the crucible and absorbing it, then the rubber under regulated that conducted heat, making the cooling process faster. By replacing the crucible to various positions in the mat and touching its previous position, by the time that all heat has been dissipated from the crucible, it can now be transferred to a dessicator. Since it is just previously heated, the switching from a hot temperature to a cooler temperature, the water vapor that is in the air can project into the crucible, and condensate. This event is what we are trying to avoid, so in this case, the dessicator is used to get rid of water molecules to take part in the weighing process. After such time that is in the dessicator, the crucible is now weighed with the cover. This process is repeated until the mass of the crucible is constant to 0.3 mg. While the determination of the constant weight of the crucible is in progress, the original purpose of the experiment can be started. By getting about 0.60 g of the unknown sample in a 400mL beaker, the solid is diluted with water and 3M HCl. This should be done under the fume hood since there might be unnecessary reactions that might bring out fumes that are harmful if released to the working environment. If the solution contains impurities that cannot be further dissolved, filter through normal filter paper. After this, put 5mL of nitric acid (HNO3) to the solution and heat it to a boil, for 5 minutes. By putting the beaker to the rubber mat, regardless of temperature, we dilute the solution to 200 mL. This step is to be done under no confusion that we are going to dilute it to a total of 200 mL, not dilute it with 200 mL of distilled water, as this will bring up errors in the final result. After this, 3M ammonia (NH3) is qualitatively added until such time that the solution is basic. The basicity of the solution can be determined with the litmus paper. It need not be on a certain pH; nevertheless its basicity is what is only important. This step will cause the solution change from yellow to a yellowish white, and there would be coagulation of the precipitate, or the colloidal form of the precipitate. The precipitate that can be seen is in now in the formula Fe2O3xH2O, meaning its hydrate molecules are not specifically known. By continuing the process, the precipitate that is formed is digested to the solution by letting it boil for another 30 minutes. This is done primarily because of the missed out ions in the solution, and by digesting it any other ions that were not precipitated out (hence called the coprecipitates) will now form and join the precipitate.

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CHE130L Analytical Chemistry Laboratory

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON While the precipitate has not yet precipitated, the filtration set-up is then assembled. The filter paper used is a coarse, ashless filter paper (Whatman 41, 110-mm diameter). This is not the same as the regular filter paper that is used when filtering impurities. We are using an ashless filter paper since an ordinary filter paper will combusted but its remains will not be disintegrated into the atmosphere, wherein the ashless paper is. The net effect of this is when you will be using a regular filter paper, and then the weight of the ignited substance will Figure 4. Filtration set-up. account the burnt weight of the filter paper, though not that accurate since some of its ashes might be disintegrated into the air, or a similar event that would rise to that. To make the filter paper stick into the funnel, wet it with distilled water. After the precipitate has been settled, the filtration process can be started. Regardless of its temperature, one can already filter even though it just came off from heating. Also, the heat from the solution helps since the solution is less dense, and therefore its viscosity (or the resistance to the relative flow speed) is low, therefore the solution will be filtered up faster than what it should be when it is at room temperature. The excess solution (or the supernatant) is to be decanted first, using the stirring rod. Be careful not to splash, spill, splatter or pour the liquid 1 cm higher than the funnel, for the liquid might bring out some of the precipitate and be left out when spilled or when anything above happens, making the error bigger. When the supernatant liquid is decanted to a close, transfer the precipitate quantitatively using a rubber policeman, fixated on the stirring rod. When there is still precipitate on the Figure 5. Decantation. beaker, pour the supernatant liquid on it all over again, reform the solids that was all over in the beaker, then re-filter. After the entire solid has been transferred, wash with pre-prepared hot ammonium chloride (NH4NO3) in the sides of the filter paper to further center the filtrate for lesser work in the next step. After all or little of the supernatant liquid is drained from the filter paper, carefully lift the paper from the funnel and fold it, and putting it to the crucible that has been weighed to constant mass, as shown. The filter paper must be carefully removed from the funnel where it has been stuck, as to Experiment 6: Gravimetric Determination of Iron 10 | P a g e

CHE130L Analytical Chemistry Laboratory IX.

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON where the filter paper must not be torn down during this step. Position the crucible to the heating process again, as shown in Figure 2. Heat the set-up to low flame. Do not cover the crucible as the ignition of the precipitate inside will require a substantial amount of oxygen, and the water that has not been drained will evaporate. When the precipitate and crucible are already dry (by inspection or by checking), turn the burner to full heat to burn the filter paper. After such time that the filter paper is burned, the gelatinous red precipitate now turned into a black powdery substance, which is hence known as rust, or Fe2O3. By Figure 6. Precipitate ignition set-up. inflaming the crucible for 15 minutes to ensure complete ignition of the iron oxide, it was then allowed to cool at room temperature via the same conditions when determining the constant mass of the crucible, then weighing it. By repeating ignition, cooling and weighing until the successive weighing that comply agree to 0.3 mg, the weight of the iron oxide can be computed through weighing by difference and finally getting the percentage iron of the sample by the formula:
( )

SUMMARY AND CONCLUSIONS By following the steps involving gravimetric analysis, this experiment concluded the concepts that involves on this classical analysis method. By having an unknown compound with an iron composition, it was prepared with an acid-base reaction to form a gelatinous precipitate which is reddish. After digesting it, it will be filtered by a coarse, ashless filter paper, as to avoid any irrelevant weight being in the final procedure. By continuous ignition and getting a constant weight, the final form, which is rust, is now used as to get the gravimetric determination of iron, which the percentage is computed to be 20.60%, which is within the range of how the theoretical weight will be in this experiment. Errors should be in particular be very much avoided, since every step in the experiment will provide crucial inconsistency with the final form of the sample when errors are introduced for they are very sensitive, even the slightest of errors would cause a dramatic change since the values that we are talking of here is significantly small, and putting a small error to a small range would by ratio give you a bigger ratio than what you expected.

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CHE130L Analytical Chemistry Laboratory X. POST LAB QUESTIONS 1. Answer:

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON

What is the effect of prolonged digestion? Answer: Digestion is referred to as the need to dissolve or dissolute a colloid, and subject it to reform again in a much bigger state than what it was before, an event that we call as recrystallization. During rest comes the completion of coagulation for solids with colloidal reduction of the surface and thus there will be less adsorption than it would normally be, therefore flocculation occurs, swelling the existing crystals. If this process is prolonged, then we could get all the other ions that we missed out (or the coprecipitates) that is in the solution that is unprecipitated, so we could get a lower percentage difference.

2. What is the purpose of using an ashless filter paper? Answer: We have to use an ashless filter paper since the weight of an ordinary filter paper will contribute to the overall weight of the dried precipitate, which is undesirable because it will introduce a systematic error in the process. An ashless filter paper burns out to become tiny ashes that deteriorate in contact with air (which is proved by our group as to which we burned an ashless filter paper, that disintegrated in the air leaving no clumps of ashes behind), therefore leaving out only the filtrate alone. 3. Why is filtration of a gelatinous precipitate done while the solution is still hot? Answer: The filtration of a gelatinous precipitate that is hot will be faster than a cold one, since the solution is less dense, therefore the solution would have practically less viscosity (even though it is similar to water but is basic) and there would be greater flow in the filtration process. Also, heat helps in the coagulation of the substance, which is very much needed for the colloidal formation of the precipitate.

4. Calculate the expected amount of Fe2O3 (in g) that would be precipitated when 0.6094 g of FeCl3 is used. Calculate the percent Fe in this iron (III) oxide. ( ( ( ) ) )

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CHE130L Analytical Chemistry Laboratory Answer: XI. REFERENCES

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EXPERIMENT NO. 6 GRAVIMETRIC ANALYSIS OF IRON

5. Using the expected results from #4, calculate your percent relative error. Are your errors systematic or random? Explain the sources of errors.

Any errors that were made would be random, as there are certain environmental disturbances that cannot be accounted for, and certain estimations to the measurements would arise to the discrepancy of the theoretical to the experimental values.

Christian, Gary D. 2004. Analytical chemistry (6th ed.). John Wiley and Sons Inc. Hage, David S. and James D. Carr. 2011. Analytical chemistry and quantitative analysis. New Jersey: Pearson Prentice Hall. Harris, Daniel C. 2003. Quantitative chemical analysis. (6th ed). New York: W. H. Freeman and Company. Skoog, Douglas et. al. 2004. Fundamentals of Analytical Chemistry (8th ed.). Singapore: Thomson Learning.

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