Experiment 21 Complexometric Titration

Purposes
1. To learn the method of preparation and standardization of EDTA standard solution 2. To know the basic procession of complexometric titration 3. To rasp the applications of chrome black T or !"lenol oran e indicator #. To learn the applications of complexometr" to determine the concentration of metal ions in unknown sample solutions

Principle
The complexin a ent of EDTA or $ #% is the abbre&iation of eth"lendiaminetetraacetic acid. And the water soluble disodium salt of EDTA '(a 2$2%)2$2*+, as a substitute, is widel" emplo"ed in titrimetric anal"sis. -ince the concentration of EDTA will be chan ed in the impure distilled water, the EDTA standard solution are usuall" prepared b" indirect preparation and standardized with primar" substance in the precisel" experiment, thou ht the disodium EDTA can be refined to a primar" standard. The prepared EDTA solution should be stored in pol"ethene bottles in order to a&oid the EDTA react with the traces of metal ions "ielded from the surface of lass &essels. To standardize the EDTA, there are some primar" standard substance such as purified .n, Cu, .n*, /i, CaC*3, 0 C*3, .n-*#)1$2* ect, and the .n, .n* and CaC* 3 are usuall" the applications. 2n order to reduce the s"stemic errors, the conditions of determinin a sample should be the same as the conditions of standardizin EDTA as possible. 2f, for example, the unknown ions ,such as /i33,.n23, 4b23, Al33, and so on, are determined, the EDTA solution should be ad5usted to p$ 6 7, and !"lenol oran e used as indicator, then standardized with primar" standard of .n or .n*. 2f the Ca23, 0 23 ions present in a sample to be determined, the CaC* 3 should be utilized as the primar" standard, the solution to be ad5usted to about p$ 18 with ($ 39 ($#Cl buffer solution, and usin Eriochrome black T as indicator. There is, howe&er, no sharp end point could be obser&ed with calcium ions and Eriochrome black T 'E/T+. And the 0 9E/T in that of the p$ re ion shows sharp wine9red in color compare with blue of the free indicator at the end point. -o the 0 C*3 can be used as an ideal primar" standard substance. Traces of man" metals, e. ., :e33, Al33, Cu23, .n23, 4b23, ect, will interfere the determination of Ca23 and 0 23 or water hardness usin Erio. T indicator. Their interfere can be o&ercome b" the addition of a little triethanolamine 'maskin the :e 33, Al33+ and (a2- 'maskin the Cu23, .n23, 4b23+.
1

The metallic ions, which in the complicated sample or react slowl" with EDTA, e. ., Al 33, can be determined b" back titration or displaced titration.

1 Determination of the hardness of water

$istoricall", ;hardness< was defined in terms of the capacit" of a water sample to precipitate soap, an undesirable =ualit". -oap is precipitated b" most cations with multiple char es. 2n natural waters, howe&er, the concentration of calcium and ma nesium ions enerall" far exceeds that of an" other metal ion> thus, hardness has come to mean the total concentration of calcium and ma nesium which expressed as c'Ca23+?mmol)@91. The determination of hardness is a useful anal"tical process for measurin the =ualit" of water for household and industrial uses. The importance for the latter is due to the fact that hard water, upon heatin , precipitate calcium carbonate, which then clo s boilers and pipes. Aater hardness is ordinaril" determined b" an EDTA titration after the sample has been buffered to a p$ of 18, and Eriochrome black T ser&es as the indicator. To determine the indi&idual Ca 23 or 0 23, the second sample is ad5usted with the addition of (a*$ to precipitate 0 '*$+2, then add the Cal9red indicator which onl" combines with the part of Ca23 ions to form a red complex .After that, use EDTA standard solution to titrate the Ca 23 of the water sample solution. EDTA will usurp the Ca 23 inos from the complex deri&ed from Ca23 ions and the cal9red after it combine with all free Ca 23 ions in the solution because it can form a more stable colorless complex with ions than the cal9red. :inall", the color of the solution turn blue with all the free cal9red released from the red complex deri&ed from Ca 23inos and the cla9red at the end point of the titration.Thus the Ca 23 can be determined b" titratin with standard solution and the content of 0 23 ma" be e&aluated b" subtractin the amount of Ca 23 from the total hardness of the water. 2n order to reduce the s"stemic errors, the 0 C* 3 be used as primar" standard substance for the standardization of EDTA in this experiment. 1.1 Apparatus and Reagents Apparatus: Anal"tical balance, platform balance, acid buret'26 m@+, conical flask'268 m@3+, transfer pipet'28m@,26m@,188m@+, &olumetric flask'26 m@,268m@+, beaker'168 m@,268m@+, rea ent bottle '1888 m@+, raduated c"linder'6 m@,18 m@, 68 m@+, lass rod,pol"ethene bottle Reagent: (a2$2%)2$2*'s A.B.+, 3 mol)@ 1$Cl, 0 C*3's, primar" standand substance+, 8.6CEriochrome black T, p$ 18 of ($ 39($#Cl buffer solution, 28Ctriethanolamine solution, 2C(a2- solution+, Calconcarbonx"lic acid indicator, (a*$ solution'18C+,uni&ersal p$ indicator 1.2 Procedure

1. 4reparation of 8.81mol)@91 EDTA solution Aei h about 1.6 of (a2$2%)2$2* with the platform balance,put it into a clean 688 m@ beaker, dissol&e the solid with distilled water, transfer the solution to a pol"thene bottle and dilute to about #88 m@. 0ix the solution throu hout and label the bottle. 2-tandardization of sodium EDTA standard solution 4repare a standard 0 C*3 solution as follows. -cale precisel" 8.28D8.22 of primar" standard 0 C*3 which has been pre&iousl" dried at 118 into a small clean beaker, add 6 drops of water to moisten the solid and co&er with a watch lass. Add 3 m@ 3mol)@ 1$Cl solution dropwise from the mouth of the beaker. After the solid has dissol&ed, add 68 m@ of distilled water 'or deionized water+ and boil entl" for a few minutes to remo&e C* 2. Cool the solution and rinse the surface of watch lass with the distilled water spra" from a washin bottle. The distilled water rinsin the watch lass is collected to ether to the beaker. Transfer it =uantitati&el" to a 268 m@ &olumetric flask and dilute to the mark, mix the solution throu hout. 4ipet 28.88 m@ 0 C*3 standard solution into a 268 m@ conical flask, and add 18 m@ ($ 39 ($#Cl buffer solution of p$ 18 and 2D3 drops Eriochrome black T indicator. Titrate with EDTA standard solution to the point where the color chan es from wine9red to pure blue and no tin s of red should remain in the solution. Bepeat the titration twice and calculate the concentration of EDTA solution.

c'EDTA+E

m'0 C* 3 +

28.88 1888 268.88 M '0 C* 3 + V 'EDTA+

3Determination of water hardness '1+ To determine the total hardness 4ipet 68.88m@ water sample into a 268m@ conical flask, add 1D2 drops 3 mol)@ 1$Cl solution and boil entl" for a few minutes to remo&e C* 2. Cool the solution, then add 6 m@ of triethanolamine, 18 m@ ($39($#Cl buffer solution of p$ 18, 18 drops (a 2- solution, and 2D3 drops of Eriochrome black T solution. Titrate with EDTA solution until the color chan es from wine9red to pure blue. Bepeat the titration twice and accordin to the consumed &olumn F 1 of EDTA solution to calculate the total hardness of the water sample.

Total hardnessG c'Ca23 +E

c' EDTA V 1 EDTA H1888'mmol)@1+ V 'water sample

1.3 Recording and treating data

Table 1 -tandardization of sodium EDTA solution DateG TemperatureG $umidit"G 1 2 3

Experiment (o. m1 'Aei hin bottle 3 0ass of 0 C*3+? m2 'Aei hin bottle 3 0ass of 0 C*3+? m19m2 '0ass of 0 C*3+? mdetermine '0ass of 0 C*3+? 2ndicator The chan e of color at the end point of titration V'0 C*3+?m@ V Initial'EDTA+?m@ V Final 'EDTA+?m@ Vconsume'EDTA+?m@ c'EDTA+?mol)@91 c A&era e 'EDTA+ ?mol)@91 Belati&e a&era e de&iation?C

Table 2 Determination of hardness of water sample Experiment (o. 2ndicator The chan e of color at the end point of titration V'water sample+?m@ 4reparation of water sample 3mol.@ $Cl?drop /oil entl" to remo&e C*2 Triethanolamine ?m@ ($39($#Cl buffer solution?m@ (a2- ?drop V Initial'EDTA+?m@ V Final 'EDTA+?m@ Vconsume'EDTA+?m@ c(Total hardness 91 +?mol)@ c Average 'Total hardness+?mol)@91 Belati&e a&era e de&iation?C
91

188.88

188.88

188.88