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Titration

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Volumetric analysis 07.8.2015 JIAN CUI
Introduction
Volumetric analysis is one of the most basic of all analytical techniques. The aim is to measure the concentration of an analyte in a solution. The first part of the this experiment involves the calibration of an item of volumetric glassware(a pipette)by repeated measurement of the volume that it delivers.
The second part of the experiment requires that you determine the concentration of an unknown solution of phosphoric acid, using a sodium hydroxide solution of known concentration that is provided to us. In the third part, we are required to prepare a solution of hydrochloric acid and measure its concentration(standardization)by titration with sodium hydroxide solution of known concentration using neutral indicator.
Materials
Equipments: analytical balance, 500 mL beaker, wash bottle, watch glass, measuring cylinder, Gooch crucibles, Gooch crucible rubber collar, oven, hot plate, vacuum flask, stirring rod,
Chemicals: 1:1 ration HCl solution, 5M ammonia solution, deionized water, 2.0% ammonium oxalate solution, Methyl red indicator.
Methods
(1) Calculation of volume delivered by pipette
Record the room temperature indicated on the wall-mounted thermometer( we assume that the water temperature is the same as the room temperature), the volume of the pipette can be calculated from the weight of water discharged and the density of the water at water temperature.
The experiment has to be repeated 6 times. The results should be averaged and the standard deviation calculated. (2) Titration of an aliquot of phosphoric acid solution Firstly, rinse the calibrated 25 mL pipette three times with small volumes of the unknown phosphoric acid solution and deliver a 25 mL aliquot into a 100 mL conical flask.ues the calibrated delivery volume of the pipette as the quantity of phosphoric acid solution taken. Secondly, add two drops of phenolphthalein/ɑ-naphtholphthalein indicator and titrate the solution with standardized sodium hydroxide solution until the color begins to change(halfway between clear and fully violet).record the titration volume. Repeat the titration two more times. Take the average of the two accurate titration volumes. Calculate the concentration fo phosphoric acid using the known stoichiometry of the reaction.
H3PO3+3NaOH=Na3PO3+3H2O

(3) preparation and standardization of a hydrochloric a acid solution prepare 500 mL of approximately 0.1 M HCl by diluting 5.0 mL of the concentrated hydrochloric acid(approximately 10M), we must add HCl into water not add water into HCl, because the dissolving process releases heat, and a 10 mL measuring cylinder is sufficiently accurate for delivering the volume of acid. Titrate 25.00 mL aliquots of the approximately 0.1 M hydrochloric acid solution with sodium hydroxide, exactly as you did in the “titration of phosphoric acid” ,except that we should use neutral red indicator. The color change at the end point is from colorless to red.
HCl+NaOH=NaCl+H2O
(4) determination of sodium carbonate in an unknown solution firstly, replace the sodium hydroxide solution in the burette with hydrochloric acid. Then titrate 25 mL sodium carbonate in an unknown solution. Use two drops of methyl orange indicator. The color change is from orange to red.
Na2CO3+2HCl=2NaCl+H2O+CO2
Results
(1)Calculation of volume delivered by pipette trial no | 1 | 2 | 3 | 4 | 5 | 6 | mass of flask/g | 38.8380 | 29.9265 | 39.0789 | 38.8124 | 29.9230 | 38.9921 | mass of flask plus water/g | 63.7792 | 54.8050 | 63.9693 | 63.7523 | 54.7597 | 63.8453 | mass of water/g | 24.9412 | 24.8785 | 24.8904 | 24.9399 | 24.8367 | 24.8532 | tempreture/℃ | 20.7 | 20.7 | 20.7 | 20.7 | 20.7 | 20.7 | water density g/mL (1) | 0.998 | 0.998 | 0.998 | 0.998 | 0.998 | 0.998 | volume of water/mL | 24.99 | 24.93 | 24.94 | 24.99 | 24.89 | 24.90 | mean/mL | 24.94 | standard deviation | 0.0435 |

(2) Titration of an aliquot of phosphoric acid solution titration no | initial volume of burette/ mL | final volume of burette/mL | titrate volume/mL | mean | acid concentration mol/mL | 1 | 0.00 | 24.95 | 24.95 | | 0.31 | 2 | 1.30 | 25.10 | 23.80 | 24.05 | | 3 | 0.10 | 24.40 | 24.30 | | |

(3)preparation and standardization of a hydrochloric a acid solution titration no | initial volume of burette/ mL | final volume of burette/mL | titrant volum/mL | mean | acid concentration mol/L | 1 | 21.70 | 42.80 | 21.10 | | 0.93 | 2 | 0.00 | 21.10 | 21.10 | 21.15 | | 3 | 21.20 | 42.40 | 21.20 | | |

(4) determination of sodium carbonate in an unknown solution titration no | initial volume of burette/ mL | final volume of burette/mL | titrant volum/mL | mean | Na2CO3 concentration mol/L | 1 | 0.00 | 29.60 | 29.60 | | 0.55 | 2 | 0.00 | 29.70 | 29.70 | 29.70 | | 3 | 2.10 | 31.80 | 29.70 | | |

Conclusion
(1)Calculation of volume delivered by pipette
Use trial no.1 as an example, Volume of water=V/ρ=24.9412/0.998=24.99mL
Mean=(24.99+24.93+24.94+24.99+24.89+24.90)/6=24.94 so the volume of the calibrated pipette is 24.94 mL
Standard deviation=(xi-x)2n-1=0.0435
(2) Titration of an aliquot of phosphoric acid solution
H3PO3+3NaOH=Na3PO3+3H2O
Vtitrate=(V2+V3)/2
Concentration of phosphoric acid=cNaOH×Vtitrate3×Vpipette=0.31mol/L
(3) preparation and standardization of a hydrochloric a acid solution
HCl+NaOH=NaCl+H2O
Vtitrate=(V2+V3)/2
Concentration of HCl=cNaOH×VtitrateVpipette=0.93mol/L

(4)determination of sodium carbonate in an unknown solution
Na2CO3+2HCl=2NaCl+H2O+CO2
Vtitrate=(V2+V3)/2
Concentration of Na2CO3=cHCl×Vtitrate2×Vpipette=0.55mol/mL discussion The most difficult part of the experiment was to determine the endpoints. Assume the volume of one drop is 0.02 mL when we use NaOH to titrate HCl .if we still need one drop to reach the endpoint, the pH value is 4.3. and if we put one more drop after the endpoint, the pH value is 9.7. thus it can be seen that the pH value changes greatly around the endpoint. As the indicator is very sensitive, only 0.02mL NaOH can change the color greatly. According to our results, the reproducibility is acceptable. Especially the last two experiments, when I had been familiar with the operation of titration, and my partner read the volume of the burette, the deviation became very small. This is how we reduce the deviation made by human error. Secondly, to improve the reproducibility , we should always use the caliberated burette and pipette during the experiment in order to reduce the effection of systematic error. The phenolphthalein/α-naphtholphthalein indicator changes its color from pH value 8.2 to 10.0. Its color changes from red to orange. Because Na3PO3 is a weak acid salt. At the endpoint the liquid becomes an alkaline liquid. That is why we choose phenolphthalein/α-naphtholphthalein as a indicator when we use NaOH to titrate H3PO3. In general we choose different kinds of indicators according to de pH value of the endpoint of titration. The confidence intervals for the result of titrations for sodium carbonate:
Mean=(29.6+29.7*2)/3=29.67 Standard deviation=(xi-x)2n-1=0.058 when we choose 90% confidence. t=1.886(2) μ= x±t×sn=29.67±0.063 all the results are included in μ. So the confidence intervals for the result at 90%. To improve the experiment, and improve the accuracy of titration. We should use a low concentration liquid for titrate the unknown solution. Since one drop of NaOH make a big difference of the pH value around the end point. Lower the concentration of NaOH is a good way to improve the accuracy. References
1.(2015) water density, [online]; avalible: antoine.frostburg.edu/chem/senese/.../water-density.html . 2. Yun Hao Ng(2015)INDC2003 - Week 2-3 lecture3:Data Analysis_2015 page 30, UNSW: School of chemical engineering.

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