PRECIPITATION TITRATION AND ITS APPLICATION OF PERCENTAGE Cl- IN SEAWATER

IMROATUZ ZAKIYAH Chemistry Departement, Mathematic and Science Faculty, Surabaya State University miss.chubb13@gmail.com ABSTRACT: Experiment about precipitation titration and its application with purpose determine (standardize) the AgNO30,1N with NaCl as primary standard and determine the percentage of Cl- in seawater. Each of experiment repeated 3times. For first experiment we do like usual titration and got normality of AgNO3 is 0.012 N. For the second experiment we got the percentage of Cl - is 2.65%, it different with theory that the percentage Cl- of sea water is 1.902%, it maybe cause the effect of evaporation, rain fall, or the numbers of river empties into the sea of Kenjeran Beach or maybe the technical errors while titration is doing for example the volume of titran is excessed then will cause error or the slipshod in making the standard or test solution. Key Word: Precipitation Titration, Indicator, Normality AgNO3, Percentage of Cl-,

ABSTRAK: Experiment ini tentang titrasi pengendapan dan aplikasinya, yang bertujian untuk menstandarisasi AgNO3 0,1N dengan NaCl sebagai standard primer dan menentukan percentase ion klorin dalam air laut. Masing-masing perobaan dilakukan 3 kai. Pada percobaan pertama kita meakukan titrasi seperti biasa dan mendapatkan normalitas AgNO3 0.012 N dan untuk percobaan kedua kita mendapatkan prosentase ion klorin sebesar 2.65%. Prosentase tersebut berbeda dengan teori sebesar 1.902% ini mungkin dikarenakan oleh efek evaporasi, hujan, atau banyaknya muara sungai ke pantai Kenjeran atau mengkin karena kesaalahan pada saat menitrasi sample seperti banyak volume titran yang keluar, atau mungkin tidak teliti dalam membuat laruta standar atau larutan sampel. Kata kunci: Titrasi pengendapan, Indikator, Normalitas AgNO3,Prosentase Cl-

INTRODUCTION Argentometry is a volumetric analysis based on precipitation reaction with AgNO3 as standard solution. The purpose of this experiment is to standardize AgNO3 use NaCl p.a as primary standard. The production of AgNO3 itself has been done by co-as of Analytical Chemistry Laboratory. So the practican just made the primary standard solution to find out the normality of AgNO3. If the normality founded, it can be use to determine the percentage of Cl in sample of sea water.
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The purposes of the experiment are determine determine (standardize) the AgNO30,1N with NaCl as primary standard and determine the percentage of Cl- in sea water. A. Volumetric titration Volumetric (titration) is one kind of method to titrate and determine the content of acid-base in a solution based on volumetric measurement. Volumetric is 1

diferentiated on three kinds based on the type of reaction : 1. Asidi-alkalimetri (neutralization titration) 2. Oksidometri (redox titration) 3. Argentometri titration) Precipitation titration is a titration involving the formation of salt deposits that are not easily soluble between titrant and analyte. The basis required from this type of titration are achievement of a rapid equilibrium formation every time titrant added to the analyte, the absence of interference that interfere with the titration, and the endpoint titration that are easily observed. One type of precipitation titration is precipitation reactions between halide ions (Cl , I , Br ) with silver ions Ag called as argentometry. Its the titration determination of analytes in the form of halide ions (in general) by using a standard solution of silver nitrate AgNO3. Titration argentometry not only can be used to determine the halide ions but also can be used to determine the (thioalkohol), fatty acids, and several divalent anions such as phosphate PO43ion and ion-AsO43- arsenat.
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Based

on

the

indicator

and

technique

used, there are three

type of argentometry ; a) Mohr method b) Volhard method c) Fajan method B. Indicators condition for precipitation titration Indicators used for precipitation titration is very limited and should have to fulfill this requirements. 1. The discoloration has to be restricted in a range of p-function of analyte 2. The discoloration has to be a part of titration curve for analyte. (Soebiyanto,2007) C. Colored precipitate formation Mohr method is a titration use standard solution to determine the concentration of Cl- of a solution or to standardize AgNO3 use a certain primary solution. This method use K2CrO4 as indicator. The end-point of titration is reached when the colour of Ag2CrO4 brick-red.

(precipitation

Picture 1.(www.googleimage.com)

The picture above shows the color change before and after end-point of titration. Initially the color of analyte is white precipitate due to the formation of AgCl. Then color change to brick-red and titration has to be stopped. The reaction happens before and after equivalent-point reached is as follow. Before and at equivalent : Ag+(aq) + Cl-(aq) AgCl(s) (white precipitate) Ksp 1,2 x 10-10 After equivalent-point : Ag+(aq) + CrO42- (aq) Ag2CrO4(s) (reddish-brown) Ksp 1,7 x 10-12 From data Ksp above, AgCl will precipitate first (white precipitate in color). Additional drops of Ag+ then will react with CrO4 and after Ksp of Ag2CrO4 is precipitate (Vogel,1958) The use of Mohr method is very limited than volhard or fajan method. This titration is in neutral condition in pH range 6.5-10. If the solution is too acid then chromate ion will be so small to make precipitate and hard to detect the end-point of titration. While in too alkaline condition will be produced brown passed, it will make the become reddish brown.

silver okside that [precludes observations of titration, (Day andUnderwood:1994) The titration solubility to be of in AgCl the and same Ag2CrO4 is affected by temperature so all has temperature. The sunlight can destroy titration because AgCl will broke down as reaction below : AgCl Ag + ClThe success of the deposition process is strongly influenced by various factors, including temperature, solvent nature, the influence of other ions, pH, hydrolysis, and complex formation. D. Selection of indicator To minimize errors of titration, the most important stuff of indicator needed to note is about the concentration. Its different with aside-alkalimetri titration because it isnt based on the changes of pH but because this is related with the forming of precipitate then concentration of indicator is very important. The concentration of indicator has to be set up so ; [CrO42-] x [Ag+]2 >= Ksp Ag2CrO4 in equivalent point. If the concentration is too high then the end-point will happen before equivalent point. While if too small,then the end-

point will happen too far from equivalentpoint. (Khopkar,1990) E. Factors affect solubility There are some factors that affect the solubility of analyte and titrant on which have to be considered while titration is doing. a) Temperature Solubility increases with increasing temperature b) The nature of solvent Inorganic salts easily soluble in water than organic solvents such as alcohol or acetic acid. The difference of solubility of a substance in an organic solvent can be used to separate a mixture of two substances. c) Effect of same ion Solubility of sediment will be reduced if dissolved in a solution containing similar ions than in water alone

e) Effect of hydrolysis If the salt of weak acid is dissolved in water it will produce changes in the concentration of H where it will cause the salt cation hydrolysis and this experience will increase the solubility of the salt. f) Effect of ion complexes Solubility which is not easily soluble salts will increase with the formation of complexes between the ligand with the salt cations (Day and Underwood:1994) F. Application of precipitation titration A precipitation reaction can be said to be interminable if the solubility of the sediment is small enough. The concentration of analyte will be changed rapidly around its equivalent point, but to note is about how to choose the best indicator. Precipitation titration can be applicated to count the content of halide ion in a sample. For example to find out the content of Cl- in seawater taken as

d) Effect of pH Solubility of salt deposits that contain anions of weak acids is influenced by pH, and this is because incorporation of protons with anions sediment

sample. Mohr method is a common way to use, a certain volume of sea water as sample is titrated with AgNO3 standard. CrO4
2-

ion used as indicator, changing

the color of solution become reddishbrown. 4

Sea water contains 3.5% salts, dissolved gases, organic materials and insoluble particles. The presence of salts affects the physical properties of sea water (such as density, compressibility, freezing point, and the temperature at which the maximum density) The main salts contained in

Density of sea water is about 1.025 g/mL and the content of Cl- is about 1.902 %. Table salts concentration of sea water Elements Symbol Concentration (mg/L ppm) Chlorin Sodium Magnesium Sulfur Cl Na Mg S 1.95 x 104 1.077 x 104 1.290 x 103 9.05 x 102 or

seawater is chloride (55%), sodium (31%), sulfate (8%), magnesium (4%), calcium (1%), potassium (1%) and the remainder (less than 1%) consists bicarbonate, strontium and bromide, fluoride. borak of acid,

www.physicalgeography.net EXPERIMENTAL SECTION Instrumentation 1. Volumetric Flask 100 mL 2. Erlenmeyer 100 mL 3. Graduated Cylinder 10 mL 4. Beaker Glass 5. Pro-pipette 6. Picnometer

Three main

sources of salts in the sea is the weathering of rocks on land, volcanic gases and hydrothermal circulation holes (hydrothermal vents) in the deep sea. Ideally, salinity is the number of all salts in sea water, but then defined as the content of chloride. Salinity in subpolar region is low in the surface and increase of depth. While in subtropic region,salinity in the surface is higher than in the depth due to effect of evaporation. In the tropic area, salinity in the surface is lower than in the depth due to high rainfall. Seawater contain salts has the higher density than pure water. The higher the density, the greater the content of Cl- .

7. Volumetric Pipette 10 mL 8. Funnel 9. Spatula 10. Analytic Balance 11. Pipette 5

12. Burette

RESULT AND DISCUSSION b. Standardization of AgNO3 0,1N with NaCl p.a NaCl solution is used as primary standard, by weighting 0.0503 gram of white powder NaCl in 100 mL water. Then 10 mL of this solution is titrated use Mohr method. Titran is AgNO3 solution that will be standardize, analyte is NaCl the standardization primary standard, and indicator is Kalium chromate.K2CrO4 is selected as indicator because the condition of system was tend to neutral. Kalium chromat can only be used in neutral condition in which the range of pH is about 6-10. Indicator is added just before titration in order not to react with the analyte and interfere the observation of end-point titration. Initially, the NaCl solution is colorless. Addition of 3 drops of indicator makes the solution weak yellow. While drops of titran is added ,the solution starts to form white precipitate. The reaction is as following: NaCl + AgNO3 NaNO3 + AgCl (white precipitate) Erlenmeyer flask during titration should be shaken to make the observation of end-point achievements easier. Besides, Ag2CrO4 formed before endin

Materials 1. NaCl p.a. 2. AgNO3 solution 3. Seawater (sample in Kenjeran beach) 4. Aquades 5. K2CrO4 indicator 5% Procedure a) Determine

AgNO3 0,1N with NaCl Weighed 0.05 g NaCl, and then dissolved volumetric until 100ml flask, taken 10 and

entered into Erlenmeyer flask, added 10 ml aquadest and 3 drops of K2CrO4. After that titrated with AgNO3 until the color of analyte become brick red, repeated the titration until 3 times. b) Determine Percentage of Cl- in Sea Water Measured the mass of sea water with picnometer, taken 10 ml and diluted 1000 times. Ater that taken 10 ml and added with 3 drops of K2CrO4. And then titrated with AgNO3 that has standardization in previous experiment.

point can be separated so that it soluble again. After all Cl- ion in NaCl solution 6

has been reacted then Ag

will react

Basically, to reach the formation of silver chromate sediments concentration of CrO42- is as much as 0.0066 M. But this will produce strongly yellow color that makes the observation of end-point titration is hard to detect. Then if the concentration is below that number, more Ag+ will be needed to titrate and more sediments of AgCl will be formed. This white precipitate will disturb the observation of end-point titration. From the experiments, titration is stopped when the red color is still murky and theres yellow color disturbing this weak brickread color. It simplies that K2CrO4 used is about 0.006 M. Another reason is due to addition of indicator is not exactly before the titration so indicator will react first with the analyte. AgCl precipitate first because it has highest value of solubility. Then Ag2CrO4 precipitate will be formed when Ksp of Ag2CrO4 is passed.The accuracy and precisions of end-point titration can be corrected use indicator blanck. But in the experiment this act was not did. Meanwhile, due to the effects of pH affects the end-point titration, it should be checked the pH before titration. This act was neither did. Titration is repeated 3 times to compare the value of volume AgNO3 needed. Fristly calculate molarity 7

with CrO42- from indicator to produce reddish-brown color. In this time AgNO3 was right up to react with NaCl. This condition was called equivalent-point of titration on which the number of mol AgNO3 was same with the number of mol NaCl. Another reason of selecting Kalium Chromat as indicator is because the solubility of AgCl is higher than that of Ag2CrO4. So AgCl will precipitate first. This is also can be due to the different electronegatifity between AgCl and
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Ag2CrO4. The electronegatifity of Cl is higher than that of CrO42- , so the Ksp of AgCl is higher. Due to this reasons ,by adding a little drops of Indicator, expected that AgCl will precipitate first and then after all Cl- is completely reacted then a small drop of Ag+ will change the color of solution that indicates the endpoint of titration. So the equivalent-point is near to the end-point of titration. Titration is stopped when the analyte forms reddish-brown sediments. But from experiment, titration is stopped when the color becomes brick-red turbid, the red color is weak. The reaction is : CrO42- + Ag+ Ag2CrO4 (reddish-brown precipitate)

of NaCl with with equation =

and calculate the normality of NaCl with equation AgNO3 with =

c. Determination Percentage of Cl- in Sea Water from Kenjeran Beach Sample of sea water taken is from Kenjeran beach located in the east of Surabaya city near Madura island. To determine the content of Cl- in sample, analyte used is sea water after 1000 times dillution. Dilution means to decrease the number of Cl- that will be titrated, so it will be more efficient and do not waste too much of AgNO3 Titran used standardization in is AgNO3 after the previous

after that calculate the Normality of equation

. It can be shown in the table below: Titration V AgNO3 N NaCl (L) 7.75 x 103

N AgNO3 (eq/L) 0.012

(eq/L)

1 2 3

7.9 x 10-3 8.05 x 103

9.38 10
-3

0.0118 0.0116

experiments (0.012 N). indicator used is K2CrO4 5%. While titration, drops of titran counted by assuming titran is equal to 0.05 mL. Before equivalent-point, the color of analyte is weak yellow due to additional of K2CrO4. And the reaction before and at the equivalent point is NaCl + AgNO3 NaNO3 + AgCl (white precipitate) While titration, the erlenmeyer flask is shaken to make the observation of end-point titration easier. The drops of AgNO3 needed is about 0.85 mL (around 15 drops of titran) to make the change of solution becomes reddish-brown. Altough the same method is used (Mohr method), but the color when endpoint achieved is different. In this 8 1 drops of

Mr NaCl= 56.5 g/mol So from the calculation, we got that Normality of AgNO3 is 0.0115 N. Based on the average volume of about 7.90 10 equation AgNO3 needed from experiment, its can also be found = the Normality of AgNO3 with using so we got 0.0118 eq/L.

This two ways give different value of N AgNO3. However, if its rounded then the N AgNO3 is 0.0012 anyway. So we use that that the Normality of AgNO3 is 0.0012 eq/L.

experiments, the color is more brown but less turbid. While in the previous experiment the color is more yellow and turbid. The less of turbid can be interpret due to the precipitate of AgCl formed is little as the volume of titran is little too. If compared, about 9 mL of titran needed in the first experiment while about 0.85 mL of titran needed in the second one. The end-point of titration is reached when the color is reddish-brown, easily observed because the formation of white precipitate of AgCl is not too much. The reaction in this condition is : CrO42- + Ag+ Ag2CrO4 (brick-red precipitate) After three times of titration, then the content of Cl- in the sample counted with equation 100. % =

concentration of Cl- in sea water is 1.95 x 104. So in the 10 ml of sample there are 195 mg Cl-. If the density of sea water is 1.025 gr/mL and the sample of sea water contain 10.25 g. The content of Cl- is 1.902 % from calculation with use equation % = 100%.

This value will be compared with the we then we calculate the mass of sample with equation equation =

content that we got from experiment. First = X Vsample. And , after =

Then calculate mol equivalent of Cl- with

theat we calculate the mass of Cl- in 1000 sample with equation , we times

with 1000 because sample solution than diluted 1000 times and picked up 10 mL as analyte. So it simplies that mass of Clin sample is equal to 1000 times mass 0f Cl- in Erlenmeyer flask. This method is called aliquot.
Titration 1 2 3 V AgNO3 (L) 7.7 x 10-4 9.0 x 10 8.5 x 10
-4 -4

The

volume of AgNO3 needed it shown in the table below. Firstly we need to find out the density of sea water with use equation and we got 1.19988 g/ml. This is higher enough than the =

Mass of sample (g) 11.998

%Cl- in sample 2.27 2.93 2.76

value

commonly standard density of sea water taken from www.physicalgeography.net (1.025 gr/mL) , shows that the sample contains high concentration of salts. If we calculate the commonly standard content of Cl- in sea water from data we got from www.physicalgeography.net , then

Mr NaCl= 35.5g/mol, N AgNO3 = 0.012 N

From the experiment that has been done,the average value is about 2.65 % The value is higher than the commonly standard of Cl- content in sea water compared namely 1.92%. However, this results is comparable with the high value of sea water density.The result shows that Cl- content in sea water sample from Kenjeran beach is 2.65%, and higher than standard value of sea water from data of www.physicalgeography.net salinity. That high salinity of sample taken can be due to the effect of evaporation, rain fall, or the numbers of river empties into the sea of Kenjeran Beach or maybe the technical errors while titration is doing for example the volume of titran is excessed then will cause error or The slipshod in making the standard or test solution CONCLUSSION AND SUGESSTION Based on data analysis and discussion above, we can conclude: 1. The Normality of AgNO3 got from the experiment was 0.012 N 2. The percentage (content) of Cl in sample of sea water taken from Kenjeran beach was 2.65%
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And the suggesstion from the writer are: 1. Be careful when diluting sample, definite the dilution exact the sign, because when the dilution more than the sign it will influence the value of percentage Cl-. 2. Be careful when standardization the AgNO3 if the volume of titran is excessed then will cause error in the second of expiment..

namely

1.92%. So the Kenjeran Beach has high ACKNOWLEDGMENT We gratefully acknowledge to

analytical chemistry lecture for providing experimental handbook that guide us to do this experiment. And also to Co-as of laboratory that help us when doing this experiment.
REFERENCE Day RA. Jr and Al Underwood.1992. Analisis Kimia Kuantitatif, sixth edition.Jakarta : Erlangga. Poedjieastoeti, Sri, M.Si, dkk. 2011. Panduan Praktikum Kimia Analitik Dasar I. Surabaya : Analytical Chemistry Laboratory of FMIPA,UNESA.

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Soebiyanto,dkk.2007.Review on argentometry mohr.

paper,

controlled indicator concentration

Vogel A.I. 1958, A Texk Book of Quantitative Inorganic Analysis, Second Edition,Longman Group Limited : New York. Sam. 2011. 2011/10/29/ Halogen. accessible 20 http://samadaranta.wordpress.com/ November 2011 at 21.00 Author. 2011. Physical and Chemical Characteristic of Seawater. http://www.physicalgeography.net/ fundamentals/8p.html accessible 20 November 2011 at 21.05

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