Experiment No. 3: Determination of Mixed Alkali I.

Abstract Neutralization titration involves chemical reaction between an analyte and a standard solution. It is used to determine the concentration of the analyte, which are acids or bases. In the analyte solution, indicators are usually added to determine the chemical equivalence point due to its ability to change color at or near that point. The determination of carbonate, bicarbonate or hydroxide of the given sample is the aim of this experiment. The stoichiometric sum of the base concentration of carbonate and its bicarbonate is the alkalinity of the solution, which can be determined by titrating the sample with standardized HCl. Two titrations are to be performed in the experiment, the first is with phenolphthalein, an alkaline range indicator and the other is bromocresol green, an acid range indicator. HCl is the standard solution that will be used since it is very stable in dilute solutions and it undergoes complete dissociation in water. It is to be standardized against a pure Na2CO3 solution. After titration, the volume of acid used would help in determining the analytes present in the sample. After 3 trials, the %(w/v) of NaOH was 0.1288%. The average standard deviation is 0.001155; the relatve standard deviation is 0.8963. The true value for the i sample is 0.1200%w/v NaOH and the relatve error was 9.0900. II. Keywords: mixed alkali systems, double indicator method, double titration method, neutralization titration, carbonate, bicarbonate, hydroxide III. Introduction Through neutralization titration, the concentration of analyte, which are either acids or bases or are convertible to such species by suitable conditions, can be determined. Indicators are usually used to indicate the point of equivalence in a neutralization titration. They are added to the analyte solution and are expected to produce a physical change, which will signal the endpoint of titration. This type of titration requires two titrations, one is with phenolphthalein, a base range indicator and the other one is with methyl red or bromocresol green, an acid range indicator. The volume of the acid titrated will help in determining the composition of the sample. The standard solution that will be used is HCl. HCl is known as a strong acid and is very stable specially in its dilute solution since it completely dissociates in water and its hydrogen ion has a very high stability. Aside from that, its chloride ion does not form insoluble products with the cations present in the solution. The experiment requires the standardization of HCl against weighed quantities of sodium bicarbonate. Due to its hygroscopic nature, sodium bicarbonate should be dried and kept in a dessicator. The Carbonates and Bicarbonates of alkali mixtures are the salts of a strong base and a weak acid and are soluble in water making them important industrial chemicals. Carbonate mixtures may contain Na2CO3, NaHCO3 and NaOH either alone or combined with the others. Only 2 components are allowed to coexist since the third component would be consumed or eliminated in the reaction. There are 5 possible systems that can exist: Na2CO3 alone, NaOH alone, NaHCO3 alone, Na2CO3, & NaHCO3, and Na2CO3,& NaOH. In this experiment, it is important to note the reaction involved in the standardization of HCl solution: CO3 2- + 2H+ H2CO3 The reactions involved in the analysis of the unknown are: Na2CO3 + HCl NaHCO3 + NaCl NaOH+ HCl NaCl + H2O NaHCO3 + HCl CO2(g) + H2O + NaCl IV. Experimental A.Preparation of 0.1 M HCl For the preparation of 0.1 M HCl, 9.85 ml of concentrated HCl was mixed into a 500-ml beaker with 300 ml of CO2 -free distilled water. The solution was mixed then transferred to a 1 L bottle and was diluted with enough CO2-free distilled water to make a 1-L solution. B. Standardization of 0.1 M HCl Five grams of primary standard grade Na2CO3 was dried at 110C for 2 hours and placed in a dessicator. Three 0.20- 0.21 gram samples were weighed by difference and transferred to three labeled 250 ml Erlenmeyer Flasks. Each of the samples was dissolved in 25 ml CO2 - free distilled water and later on added with 2 drops of bromocresol green indicator. The sample was then titrated with the previously prepared 0.1 M HCl solution until the analyte has changed its color from blue to green. After titration, the analyte was boiled gently for two minutes. The solution was covered with a watch glass to retard further absorption of CO2 and was allowed to cool. Upon cooling, there should be recurrence of blue color. Titration was continued until a sharp blue to green color change was observed. The volume of the HCl used was recorded and the procedure was repeated for the remaining samples. C. Analysis of the Unknown Three 0.20-0.21 g samples of the unknown were weighed by difference and transferred into three

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labeled 250-mL Erlenmeyer flasks, containing 25ml CO2 - free distilled water. The mixture was swirled and was added with 2 drops of phenolphthalein indicator after boiling for a few minutes. After adding phenolphthalein, the solution was immersed in an ice-water bath and was titrated slowly while swirling it constantly until the pink color disappeared. The volume of HCl used was recorded and the solution was removed from the ice water bath. Immediately, two drops of bromocrescol green indicator were added and titration was continued following the same steps in the standardization procedure. Again, the volume for bromocrescol green endpoint was recorded. The entire procedure was repeated for three trials. The %(w/v) Na 2CO3 and NaOH were calculated. V. Results Amount of concentrated HCl= 9.85ml M1 V1=M2 V2 (10.15M) (X) = (0.1M) (1L) Standardization of HCl Solution TRIAL Wt. Na2CO3 VHCl (g) (ml) 1 0.2051 30.60 2 0.2006 30.80 3 0.2151 31.20 Average 0.1265 Molarity MHCl= 0.1265 M


double titration method and the other one is through double indicator method. The latter one is used for this experiment. In this experiment, HCl is used as the standard solution for the titration. 9.85ml of concentrated HCl was used to make 1 liter of 0.1M HCl. HCl is a strong acid that is very stable in its dilute solution on account of the high stability of hydrogen and because of its complete dissociation in water making it very ideal for titration. The chloride anions of HCl do not form insoluble products with the cations present in the system. Also, HCl in its dilute form of HCl is not a strong oxidizing and reducing agent. The reactions involved in the standardization of HCl would be : HCl H+ + Cl 2+ CO3 + 2H H2CO3 It can be seen that there is a 1:2 mole ratio between HCl and CO32- which will help in computing for the molarity of the HCl. Na2CO3 crystals were used for the standardization of HCl. Na 2CO3 is very hygroscopic thus it needs to be dried for 2 hours and be stored in a dessicator. A variety of indicators can be used to titrate Na2CO3 such as phenolphthalein, methyl red or bromocresol green. In the experiment, bromocresol green was used instead of methyl red for better determination of the pH range. Phenolphthalein is a base range indicator, which turns pink in basic solutions (having pH greater than 8) and colorless in acidic solution (having pH less than or equal to 8). Methyl red is an acid range indicator, which turns red in acidic solutions (having pH less than 4.4) and yellow in basic solutions (having pH greater than 6.2). Bromocresol green is an acid range indicator between pH 4.5 (yellow) and 5.5 (blue) that turns slightly green in between. For the standardization process, the indicator used was the bromocresol green. There are five possible combinations or mixtures of the three alkalis. No more than two of the three constituents may be combined for reactions will eliminate the third. Mixing NaHCO3 results in the formation of Na2CO3 until one or the other, or both of the original reactants is used up. If NaOH is used up, the solution will contain Na2CO3 and NaHCO3; if NaHCO3 is depleted, Na2 CO3 and NaOH will remain; if equimolar amounts of NaHCO3 and NaOH are mixed, the principal solute species will be Na2CO3 . HCO3- and OH- neutralize each other in a reaction that is why Carbonate, bicarbonate and hydroxide ions cannot coexist with one another in a solution. 2HCO3 (aq) + OH (aq) CO3 (aq) + H2O

MHCl 0.1265 0.1229 0.1301

Analysis of the Unknown TRIAL VHCl VHCl (ml) (ml) Bcg endpt Pth endpt 1 6.3 0.3 negligible 2 6.4 0.3 negligible 3 6.4 0.5 negligible Average 0.1288 %NaOH %w/v NaOH= 0.1257%

% (w/v) NaOH 0.1275 0.1295 0.1295

VI. Discussion The goal of the experiment is to be able to determine the mixed alkali of the given sample. An alkali is a combination of carbonates, bicarbonates or/and hydroxides that neutralizes an acid, which then forms water and salt. They are soluble in dilute solutions. There are two known methods in determining the composition of an unknown sample. One is through

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The 1 case contains Na2CO3 only.

st

Na2CO3 + HCl
Na2CO3 + HCl + HCO3 + H30 NaHCO3 + NaCl H2CO3 + H2O

NaHCO3 + NaCl

There are two endpoints in this case wherein the volume of the titrant (HCl) for the phenolphthalein endpoint will be equal to the volume of titrant(HCl) from phenolphthalein to the bromocresol green endpoint. The 2nd case contains Na2CO3 and NaOH.

NaHCO3 + HCl NaCl + H2O + CO2 ** H2O + CO2 H2CO3 The phenolphthalein titration volume is less than 2the bromocresol green titration. CO3 was first titrated and became HC03 in the phenolphthalein titration. The HCO3 adds up to the HCO3 from the NaHCO3 originally in the sample, resulting to a larger bromocresol green titration volume. The 4th case contains NaOH only.

Na2CO3 + HCl NaOH + HCl

NaHCO3 + NaCl NaCl + H2O

HCO3- and OH- are both present in the sample and will neutralize. OH will be consumed first and its neutralization would cover for the phenolphthalein titration. HCO3 will be neutralized during the bromocresol green titration. The titrant needed to reach phenolphthalein endpoint is greater that the volume of titrant needed for bromocresol end point.

NaOH + HCl NaCl + H2O This is a strong acid-striong base titration. NaOH is the only alkali present so it has only one equivalence point. Bromocresol green is not needed anymore since neutralization of NaOH is reached during phenolphthalein titration The 5th case contains NaHCO3 only.

The 3rd case contains Na2CO3 and NaHCO3.

NaHCO3 + HCl NaCl + H2O + CO2 ** H2O + CO2 H2CO3 The volume of phenolphthalein titration is zero because the HCO3- in the solution was too acidic

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that the indicator wasnt able to detect it. The volume of HCl is equal to the volume of NaHCO3 after bromocresol green endpont.

measured very well or if the standardized HCl is exposed to the environment for a long time. The students should take note of their titration techniques so as to be aware whether they have already reached the endpoint. Always use CO2-free distilled water so as to avoid contaminants. Cover all reagents if necessary to avoid exposure to contaminants. Unstability of the carbonate mixtures may occur due to CO2 exchange with the environment. One must also be well-acquainted with the procedures of the experiment. DOUBLE TITRATION METHOD Constituents: Volumes: NaOH Vpth=Vbcg Na2CO3 Vpth= Vbcg NaHCO3 Vpth=0; Vbcg>0 NaOH+Na2CO3 Vpth> Vbcg NaHCO3+Na2CO3 Vpth< Vbcg DOUBLE INDICATOR METHOD Constituents: Volumes: NaOH Vpth>0; Vbcg=0 Na2CO3 Vpth=Vbcg NaHCO3 Vpth=0; Vbcg>0 NaOH+Na2CO3 Vpth>Vbcg NaHCO3+Na2CO3 Vpth<Vbcg VIII. References Hargis, L. Analytical Chemistry: Principles and Techniques. Prentice Hall (1988) Skoog, et al. Fundamentals of Analytical Chemistry. 8th edition http://www.csudh.edu/oliver/demos/carbnate/carbna te.htm http://coryw.people.cofc.edu/3Titrimetric%20Determination%20of%20Sodium%20 Carbonate.pdf?referrer=webcluster& http://resources.edb.gov.hk/~science/pdf/sDL_4_Do uble_indicators.pdf http://shailendrakrchemistry.files.wordpress.com/20 09/11/double-indicator-theory.pdf

For the first titration, the indicator used is phenolphthalein. 2 drops of phenolphthalein were added to 25 ml of the diluted solution of the unknown sample. The solution turned pink indicating that it may contain sodium carbonate, sodium hydroxide or a mixture of both. It was then titrated with the standardized HCl until the solution turned colorless. This titration is a neutralization reaction making it exothermic. Since carbon dioxide is more soluble in lower temperature, having a high temperature would lead to the escape of carbon dioxide from the system. Carbon dioxide comes from the carbonates, so when it escapes from the system in its gaseous form, the carbonates would also decrease. When that happens, discrepancies would become inevitable. So the titration with phenolphthalein until the disappearance of the pink color was done in an ice bath to make sure that all forms of carbonate remains intact. The second indicator used after the titration with phenolphthalein is the bromocresol green. The solution will turn blue upon the addition of this indicator. It will then be titrated with HCl and was boiled after the solution turned green. This was done to destroy the buffer. Titration will be continued until the reappearance of green color. VII. Conclusion and Recommendations In order to determine the components of a mixed alkali solution in a neutralization reaction, one must analyze the results of the titrations- compare the volumes of the titrant in phenolphthalein and bromocresol green endpoints. The groups unknown only had NaOH as constituent. This was concluded through the negligible volume of HCl with the bromocresol green endpoint. In our results, the volume of HCl in phenolphtalein endpoint is huge and there is negligible amount of HCl in the bromocresol green endpoint. We were then able to conclude that the sample only contains NaOH. Discrepancies in the data resulted from various factors like improper lab techniques or over titration. The reagents used may also result to errors if not

I hereby certify that I have given substantial contribution to this report.

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