EXPT.

6 TURBIDIMETRIC DETERMINATION OF SULPHATE IONS IN A WATER SAMPLE

Structure
6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 Introduction
Objectives

Turbidimetric Determination of Sulphate Ions in a Water Sample

Turbidimetry Principle Requirements Solutions Provided Procedure Observations and Calculations Result Precautions

6.1

INTRODUCTION

You have so far learnt about and performed a number of experiments based on spectrophotometry. These experiments pertained to the determination of the concentrations of inorganic or organic species and a physical constant for an organic molecule. You would recall that in the previous experiments using spectrophotometer you were required to measure the absorbance of the solutions and determine the concentration of the analyte from it using Beer-Lamberts law. In turbidimetric determinations, the spectrophotometer is used to measure the percent transmittance which is related to turbidity. In this experiment you would learn about the turbidimetric determination of sulphate ions in a sample of water. You know that water samples from natural sources contain dissolved sulphates. For example, the presence of sulphate in rain water may be traced down to the oxidation of sulphur obtained as a result of the combustion of coal or petroleum oil. The sulphur trioxide so obtained dissolves in rain water to form sulphuric acid. The presence of sulphate can also be due to dissolved minerals or from some other source. In the turbidimetric determination, the sulphate ions present in the sample are converted into a suspension of barium sulphate which is then determined turbidimetrically. You would be using a spectrophotometer to determine the turbidity of a solution. When carefully performed, the turbidimetric method provides reproducible results for such an important determination. This method is much faster and sensitive as compared to the commonly employed gravimetric determination. In the next experiment you would learn about the application of IR spectrometry in the determination of functional group of organic compounds.

Objectives
After studying and performing this experiment you should be able to:

explain the principle of turbidimetry, explain the principle underlying turbidimetric determination of sulphate ions in a water sample, enumerate the general factors that may affect the results of a turbidimetric determination, observe due precautions while performing the turbidimetric determination of sulphate ions, and adapt the method for other turbidimetric determinations. 1

SpectroscopicMethods Lab.

6.2

TURBIDIMETRY

You have learnt about different spectroscopic methods of analysis in the MCH-003 course. However, you have not learnt about turbidimetry. Let us learn about the meaning and the principle of turbidimetry. You know that some of the insoluble compounds in small amounts may be obtained as stable suspensions. When light is passed through such a suspension, the incident electromagnetic radiation interacts with the suspended particles and a part of it gets dissipated due to absorption, reflection and refraction. The unabsorbed part of the radiant energy gets transmitted. The intensity of the transmitted radiation is a measure of the turbidity of the solution and is a function of concentration of the dispersed particles in the suspension. The percent transmission can be mathematically converted into turbidance (S) as per the following equation. S = logT = 2 log%T (6.1) Where, T is the transmittance and %T refers to the percent transmittance. The measurement of transmittance of a fine suspension as a measure of the turbidity of the solution forms the basis of turbidimetry. The relationship between the turbidance of the suspended particles and its concentration is semi-empirical in nature. Therefore, it is necessary to construct a calibration curve for turbidimetry. The calibration curve is obtained by using different dilutions of the standard solution and measuring their transmittance under identical conditions. This curve is then used to determine the sample concentration whose transmittance is also measured in the same way as the standards. The intensity of scattered light depends on the number and size of the suspended particles. Therefore the precipitate must be very fine so that it does not settle rapidly. The accuracy of the results depends a great deal on the reproducibility of the turbidity formed. Therefore, while preparing the turbid solution; utmost care is necessary to ensure reproducibility of turbidity. Further, for accurate and reproducible results with turbidimetric techniques, it is critical that factors such as temperature, time and rate of stirring, and time of standing of suspension before measurements, be as uniform as possible for the standard solutions and the analyte samples. The following conditions must be ensured for the reproducibility of turbidity;

The ratio of concentration of the reactants must be uniform. The order of addition, rate of addition, rate of mixing, and time delay between preparation of the suspension and the measurement of turbidity must be same for the standards and the unknown samples. The presence of other salts (matrix) must be same for the standards as well as the samples. Temperature must be maintained.

6.3

PRINCIPLE

Barium is the only common ion which forms a precipitate with sulphate in highly acidic solutions.

In the turbidimetric determination of sulphate ions in a water sample, the sulphate ions are converted to a suspension of BaSO4 under controlled conditions. The sulphate ions present in the sample are precipitated by the addition of a highly acidified solution of barium chloride to form the suspension as per the following equation.
SO 2 + BaCl 2 BaSO 4 + 2 Cl 4

The percent transmittance of the suspension is then determined by a spectrophotometer. This is then is mathematically converted to turbidance. The turbidance of the sample solution is compared with a calibration curve drawn from standard solutions of sulphate ions.

6.4

REQUIREMENTS
Chemicals Potassium sulphate Sodium Chloride Barium Chloride Hydrochloric acid Glycerol Absolute Ethanol

Apparatus Spectrophotometer/ Filter photometer 1 Matched cuvettes 2 Volumetric flasks (1 dm3 ) 2 Conical flasks (100 cm3 ) 10 Burettes 3 Graduated pipette (5 cm3) 1 Sieves (20 and 39 mesh) 1each

Turbidimetric Determination of Sulphate Ions in a Water Sample

6.5

SOLUTIONS PROVIDED

Standard sulphate solution: It is prepared by dissolving 0.1810 g of analytical grade potassium sulphate in about 200 cm3 of distilled water taken in a one litre volumetric flask and diluting it to mark with distilled water. The standard solution so obtained contains 0.1 mg of sulphate per cm3 (100 mg per dm3 ). Sodium chloride-HCl solution: It is prepared by dissolving 60 g of analytical grade sodium chloride in about 150 cm3 of distilled water taken in a one litre volumetric flask followed by addition of 5 cm3 of Analytical grade conc. HCl and diluting it to mark with distilled water. Glycerol-ethanol solution: It is prepared by mixing one volume of pure glycerol in two volumes of absolute alcohol.

6.6

PROCEDURE
the sodium chloride -hydrochloric acid solution is added before the addition of barium chloride. This is to inhibit the growth of micro crystals of barium sulphate. the temperature and pH of the solution should be maintained. the order of addition, rate of addition, rate of addition and shaking of solution must be maintained uniform for all the standards and unknown samples. the turbidity is stabilized by the addition of glycerol-ethanol solution. the time interval between precipitation and transmittance measurement must be maintained constant.

In the turbidimetric determination of sulphate ions, it is essential that,

The following procedure takes care of the above mentioned requirements. Follow the steps given below in sequential order to perform the experiment. 1. Take 6 conical flasks of 100 cm3 capacity labelled from 1 to 6 and transfer the standard solution of sulphate ion and water in them as per the details given in column 2 and 3 of the Observation Table 6.1. You may use burettes for the purpose. Take another 2 conical flasks of 100 cm3 capacity and label them as S1 and S2 and transfer 50 cm3 each of the unknown water sample in these. You may use pipette / burette for the purpose. To another 100 cm3 conical flask, labelled as blank, transfer 50 cm3 of distilled water to prepare the blank solution. Transfer 5 cm3 of the sodium chloride-hydrochloric acid solution and 2 cm3 of glycerol-ethanol solution each to the solution in the flask labelled as S1 and the
The time at which the turbidity of each solution is measured is critical to the determination. Therefore, treat each solution individually in as similar a manner as possible and do not attempt to treat all the solutions simultaneously.

2.

3. 4.

SpectroscopicMethods Lab.

flask labelled as blank. Keep the flask (NO-S1) on a magnetic stirrer and place a stirrer bar in the solution. Turn on the stirrer and adjust the stirring rate so as to obtain a shallow vortex in the solution. Note the position of the control knob on the stirrer. The same position, i.e., the same stirring rate, is used for all of the solutions. 5. Add 0.3 g of sieved barium chloride crystals (the crystals should pass through the sieve of 20 mesh and be retained by 39 mesh sieve ) to the above solution and start the timer. Stop the stirring after one minute but allow the timer to continue. Immediately fill a cuvette with the solution and place in the spectrophotometer holder. Add 0.3 g of sieved barium chloride crystals to the blank flask also and shake to dissolve it. Measure the percent transmittance of the solution at 420 nm after an interval of 5 1 minutes after the stirring was stopped (the total time elapsed after the addition of barium chloride is 6 1min.) The percent transmittance of the solution is measured against the blank and is recorded in the column no 7 of the Observation Table 6.1. Repeat the same (steps 4 to 6) as above for the solution numbered 2 to 6 and record the percent transmittance values in the column 7 of the Observation Table 6.1. Treat the sample solutions, S1 and S2 in the same way (steps 4 to 6) and record the percent transmittance appropriately in Observation Table 6.1. Convert the percent transmittance values for the standard solutions as well as for the sample solutions into turbidance using Eq. 6.1, and record the same in column of Observation Table 6.1. Plot a graph between the concentration at X-axis (column 4) and turbidance Y-axis ( column 8) in the Fig. 6.1. Determine the concentration of sulphate ions in the given sample solution with the help of the calibration curve and report the result.

6. 7. 8.

9.

10. 11.

12. 13.

6.7

OBSERVATIONS AND CALCULATIONS

Observation Table 6.1: Transmittance/turbidance data for the standard and sample sulphate solutions. 1 S. No. 2 Vol. of Std. sulphate solution (cm3) 2 5 10 15 25 35 3 Volume of Distilled Water (cm3) 48 45 40 35 25 15 50 Water Smaple 50 50 Column 4 Conc. of standard sulphate solution (ppm) 4 10 20 30 50 70 0 ? ? 5 Vol. of NaClHCl solution (cm3) 5 5 5 5 5 5 5 5 5 6 7 8 Vol. of Percent TurbidGlycerol transmit- ance -Ethanol ance solution (cm3 ) 2 2 2 2 2 2 2 2 2

1 2 3 4 5 6 Blank S1 S2 4

Turbidimetric Determination of Sulphate Ions in a Water Sample

Turbidance 0

20

40

60

80

100

Concentration (ppm) of sulphate ions

Fig. 6.1: Calibration plot between turbidance and concentration of standard sulphate solution

The concentration of sulphate ions in solution S1 =.......ppm The concentration of sulphate ions in solution S2 =.......ppm Average =..........ppm

6.8

RESULT

The concentration of the sulphate ions in the given sample of water is found to be = .....ppm

6.9

PRECAUTIONS
Since suspended material in the sample can interfere with the analysis, it is necessary to filter suspended matter from the solution prior to the determination. Any coloured substance that absorbs radiation at the wavelength which is chosen for the analysis can also interfere. Take care to avoid any air bubbles adhering to the walls of the spectrophotometer tube.