1.

PURPOSE: The purposes of this experiment are; to settle various kind of alkalinity by indicator method to show the applicability limits of ionic-equilibrium approach in natural water systems to compute the concentration of components at the carbonate system from alkalinity values.

2. PROCEDURE: We have five samples which are; Sample 1: OH- , approx., 50 mg/L: Add 3 mL 1M NaOH solution to 997 mL distilled water. Sample 2:CO3= ,approx. ,180 mg/L :Add 3 mL 1 M NaOH solution and 3 mL NaHCO3 solution to 994 mL distilled water. Sample 3:HCO3- , approx., 180 mg/L: Add 3 mL 1M NaHCO3 solution to 997 mL distilled water. Sample 4:CO3=, approx., 180 mg/L; OH- , approx.,35 mg/L :Add 5 mL 1M NaOH and 3 mL 1M NaHCO3 solution to 992 mL distilled water. Sample 5:CO3=, approx., 180 mg/L; HCO3- , approx.,60 mg/L :Add 3 mL 1M NaOH solution and 4 mL 1M NaHCO3 solution to 993 mL distilled water. 1. We take 50 ml from the water sample. 2. We insert pH electrode from the pH meter into the beaker. Put a magnetic stirring-bar and stir the solution constantly. 3. According to the pH value we will add either phenolphthalein or methyl orange indicator. If the pH is higher than 8.3 we need to add 0.5 mL of phenolphthalein indicator. If the pH is below 8.3, 0.5 mL methyl orange indicator needs to be added. 4. We place 0.02 N H2SO4 solution in a brute. 5. We slowly add the acid from the brutte while stirring the solution. 6. For samples with pH greater than 8.3, we titrate the sample until the phenolphthalein end point that is pH 8.3 and record the volume of titrant (Vp). 7.Then add about 0.5 mL methyl orange indicator and titrate the sample at step 6 until the methyl orange end point is reached that is pH 4.5 by slowly adding the acid from burette while stirring the solution and again recording the volume of titrant (Vmo). 8.If the pH is lower than 8.3 ,we titrate the sample until the methyl orange end point that is pH 4.5 and record the volume of titrant (Vmo). 3. THEORY:

Alkalinity is the buffering capacity of a water body. It measures the ability of water bodies to neutralize acids and bases thereby maintaining a fairly stable pH. Water that is a good buffer contains compounds, such as bicarbonates, carbonates, and hydroxides which combine with H+ ions from the water thereby raising the pH of the water. Without this buffering capacity, any acid added to a lake would immediately change its pH. Alkalinity comes from rocks and soils, salts, certain plant activities, and certain industrial wastewater discharges (detergents and soap based products are alkaline). If an areas geology contains large quantities of calcium carbonate, water bodies tend to be more alkaline. (pH and Alkalinity,2004,p.3) Alkalinity is measured by titration with a strong acid. pH Until 10-11 Until 8.3 Until 4.5 Reactions H++OH- H2O H++CO32- HCO3H++HCO3- H2CO3

Phenolphthalein end point Methyl orange end point

Vp =volume of acid used to reach phenolphthalein end point Vmo=volume of acid used from p.p end point to reach methyl orange end point Approximate Concentrations of Species from Alkalinity Titration Data Condition Vp=Vmo VP=0 Vmo=0 Vmo>VP Vmo>VP (Snceyink, Jenkins, 1980, pp.173-183) Phenolphthalein alkalinity: Water that has a pH >8.3 is said to have phenolphthalein alkalinity which is alkalinity due to primarily to the presence of carbonate or hydroxide ions. Phenol. Alk. (mg/L as CaCO3) = Vp (mL)*NH2SO4*50000/mL sample Total alkalinity: The amount of acid required to react with the hydroxide, carbonate and bicarbonate represents the total alkalinity. Total Alkalinity (mg/L as CaCO3) = Vtotal H2SO4 (mL)*NH2SO4*50000/mL sample Total Alkalinity (eq/L) = [HCO3-] + [2CO3=] + [OH-]-[H+] Total Alkalinity (eq/L) = Vtotal H2SO4 (mL)*NH2SO4 /mL sample Hydroxide alkalinity: Predominant form of alkalinity CO32HCO3OHCO32- and HCO3OH- and CO32-

The sample has a high pH (pH > 10).The titration of this sample is concluded at the phenolphthalein end point. In this point hydroxide alkalinity is equal to the phenolphthalein alkalinity. Carbonate alkalinity: The samples pH is between 8.3 and 10 .The titration to the phenolphthalein end point is exactly equal to one half of the total titration .In this point carbonate alkalinity is equal to the total alkalinity . Bicarbonate alkalinity: The samples pH is usually less or equal to 8.3. In this point bicarbonate alkalinity is equal to the total alkalinity. Hydroxide Carbonate alkalinity: The samples PH is usually higher than 10. The titration from the phenolphthalein to methyl orange end point represents one half of the carbonate alkalinity. Carbonate alkalinity (mg/L as CaCO3) =2*Vmo*NH2SO4*50000/mL sample Carbonate-Bicarbonate alkalinity: The pH of sample is higher than 8.3 and less than 11. The titration to the phenolphthalein end point shows one half of the carbonate alkalinity. Carbonate alkalinity. =2*Vp*NH2SO4*50000/mL sample Bicarbonate alkalinity = Total alkalinity Carbonate alkalinity Carbonate alkalinity: C.A=2*Vmo*NH2SO4/Vsample if VP>Vmo C.A=2*Vp*NH2SO4/Vsample if Vmo>Vp C.A=2*Vp*NH2SO4/Vsample if Vp=Vmo Bicarbonate alkalinity: B.A=Vmo*NH2SO4/Vsample if Vp=0 B.A= (Vmo-Vp)*NH2SO4/Vsample if Vmo>Vp Caustic or hydroxide alkalinity: H.A=Vp*NH2SO4/Vsample if Vmo=0 H.A= (Vp-Vmo)*NH2SO4/Vsample if Vp>Vmo Calculation from equilibrium equations Equilibrium equations and charge balance (electro neutrality) in solution gives the concentrations of carbonate, bicarbonate and hydroxide. Electro neutrality is that the sum of the equivalent concentrations of the cations must equal that of the anions. Total

alkalinity is a measure of the equivalent concentration of all cations associated with the alkalinity producing anions except the hydrogen ion. Therefore, we have some equations: [H+]+alkalinity/50000 = [HCO3-] +2[CO32-] + [OH-] The equilibrium equations which must be considered are that for water and that for the second ionization of carbonic acid, [H+][CO32-]/ [HCO3-] =KA2 KA2 =10-10.3 Equations necessary for this calculation are, Kw = [H+] [OH-] Kw =10-14

Alkalinity = [HCO3-] +2[CO32-] + [OH-]-[H+] We have some equations for [HCO3-] and [CO32-]. Carbonate Alkalinity (mg/L as CaCO3) =50000[(alkalinity/50000) + ([H+]-[OH-])]/1+ ([H+]/2KA2) [CO32-] (mg/L) = Carbonate Alkalinity (mg/L as CaCO3)*0.06 Bicarbonate Alkalinity (mg/L as CaCO3) =50000[(alkalinity/50000) + ([H+]-[OH-])]/1+ (2KA2/ [H+]) [HCO3-] (mg/L) = Bicarbonate Alkalinity (mg/L as CaCO3)*1.22 (Sawyer, McCarty, Parkin, 2003, pp.550 -558) 4. DATA ANALYSS AND CALCULATIONS: NH2SO4=0.02 N Sample 1 2 3 4 5 Initial pH 11.46 10.90 9.14 11.54 10.80 Vp 13.2-6.5=6.7 21.4-14.4=7 29.328.9=0.4 48.136.4=11.7 22.715.1=7.6 pH 8.31 8.35 8.35 8.28 8.26 Vmo 14-13.2=0.8 28.921.4=7.5 36.429.3=7.1 15.1-8.6=6.5 31.922.7=9.2 pH 4.61 4.50 4.68 4.45 4.45

1- ) Ion calculations for each of the samples Sample 1: Vp=6.7 mL Vmo>= 0 [OH-] = _6.7* 0.02 =2.68*10-3 eq/L 50

Sample 2:Vp>=Vmo [CO3-2] = ____7*0.02__ =2.8*10-3 eq/L 50

Sample 3: V mo=7.1 mL Vp>=0 [HCO3-] =__7.1*0.02_ =2.84*10-3 eq/L 50

Sample 4: Vp>Vmo [CO3-2] =___6.5*0.02_ =2.6*10-3 eq/L 50 [OH-] = __(11.7-6.5)*0.02 = 2.08*10-3 eq/L 50 Sample 5: Vmo>Vp [CO3-2] = ____7.6*0.02_ =3.04*10-3 eq/L 50 [HCO3-] = (9.2-7.1)*0.02/50 = 6.4*10-4 eq/L 2- ) Calculations of all possible forms of alkalinity: Sample 1: Predominant forms: OHPhenolphthalein Alkalinity: 6.7*0.02*50000/50 =134 mg/L as CaCO3 Phenolphthalein Alkalinity= Hydroxide Alkalinity Sample 2: Predominant forms: CO32Total Alkalinity: (7+7.5)*0.02*50000/50 =290 mg/L as CaCO3 Total Alkalinity= Carbonate Alkalinity Sample 3: Predominant forms: HCO3Total Alkalinity: (7.1+0.4)*0.02*50000/50 =150 mg/L as CaCO3 Total Alkalinity= Bicarbonate Alkalinity Sample 4: Predominant forms: OH-, CO32-

Carbonate Alkalinity=2(ml H2SO4 spentmethly)*NH2SO4*50000/ml.sample as CaCO3 Carbonate Alkalinity=2*6.5*0.02*50000/50 =260 mg/L as CaCO3 Total Alkalinity =(6.5+11.7)*0.02*50000/50 =364 mg/L as CaCO3 Total Alkalinity Carbonate Alkalinity=Hydroxide Alkalinity 364-260=104 mg/L as CaCO3 Sample 5: Predominant forms: CO32-, HCO3Carbonate Alkalinity=2*(ml H2SO4 spentphenol.)*NH2SO4*50000/ml.sample Carbonate Alkalinity=2*7.6*0.02*50000/50 =304 mg/L as CaCO3 Total Alkalinity= (7.6+9.2)*0.02*50000/50 =336 mg/L as CaCO3 Total Alkalinity-Carbonate Alkalinity =Bicarbonate Alkalinity 336-304=32 mg/L as CaCO3 3- ) Calculation of the ion concentration by using the initial pH and alkalinity values Sample 1: initial pH=11.46 [H+] =10-11.46 =3.46*10-12 M alkalinity=134 mg/L Kw = [H+]*[OH-] =10-14 10-14 =3.46*10-12*[OH-] [OH-] = 2.9*10-3 M

Sample 2: initial pH=10.90 [H+] = 1.26*10-11 M alkalinity = 290 mg/L [OH-] = 8*10-4 M [H+][CO32-]/ [HCO3-] =KA2 10-10.3 =1.26*10-11[CO32-]/ [HCO3-] [CO32-]/ [HCO3-] = 4 [H+]+alkalinity/50000 = [HCO3-] +2[CO32-] + [OH-] (1.26*10-11)+290/50000 = [CO32-]/4+2[CO32-] + (8*10-4) [CO32-]=2.2*10-3 M Sample 3: initial pH =9.14 [H+] =7.2*10-10 M alkalinity =150 mg/L [OH-] =1.4*10-5 M [H+][CO32-]/ [HCO3-] =KA2 10-10.3 =7.2*10-10[CO32-]/ [HCO3-] [CO32-]/ [HCO3-] =0.07 [H+]+alkalinity/50000 = [HCO3-] +2[CO32-] + [OH-] 7.2*10-10+150/50000 = [HCO3-] +0.14[HCO3-] +1.4*10-5 M [HCO3-] =2.6*10-3 M

Sample 4: initial pH= 11.54 [H+] =2.8*10-12 M alkalinity=364 mg/L [OH-] =3.6*10-3 M [H+][CO32-]/ [HCO3-] =KA2 10-10.3 =2.8*10-12[CO32-]/ [HCO3-] [CO32-]/ [HCO3-] =18 [H+]+alkalinity/50000 = [HCO3-] +2[CO32-] + [OH-] 2.8*10-12+364/50000 = [CO32-]/18+2[CO32-] +3.6*10-3 M [CO32-] =1.8*10-3 M Sample 5: initial pH =10.8 [H+] =1.6*10-11 M alkalinity =336 mg/L [OH-] =6.25*10-4 M [H+][CO32-]/ [HCO3-] =KA2 10-10.3 =1.6*10-11[CO32-]/ [HCO3-] [CO32-]/ [HCO3-] =3 [H+]+alkalinity/50000 = [HCO3-] +2[CO32-] + [OH-] 1.6*10-11+336/50000 = [HCO3-] +6[HCO3-] +6.25*10-4 [HCO3-] =8.7*10-4 M [CO32-] =2.6*10-3 M 5. DISCUSSIONS AND CONCLUSIONS 1-) Sample 1: 1st [OH-] = 2.68*10-3 eq/L 3rd [OH-] = 2.9*10-3 M 2.9*10-3 mole/L*1 eq/mole =2.9*10-3 eq/L The error is less than 5%. Sample 2: 1st [CO3-2] =2.8*10-3 eq/L 3rd [CO3-2] =2.2*10-3 M 2.2*10-3 mole/L*2 eq/L =4.4*10-3 eq/L The error is more than 5 %. Maybe we did not measure the Vp properly. Sample 3: 1st [HCO3-] = 2.84*10-3 eq/L 3rd [HCO3-] =2.6*10-3 M (=eq/L) The error is less than 5%. Sample 4: 1st [OH-] =2.08*10-3 eq/L The error is more than 5%. Maybe we did some measurement errors. 1st [CO32-] = 2.6*10-3 eq/L The error is more than 5%. 3rd [CO32-] =1.8*10-3 M (=3.6*10-3 eq/L) 3rd [OH-] =3.6*10-3 M (=eq/L)

We have some measurement errors. Sample 5: 1st [HCO3-] =6.4*10-4 eq/L The error is more than 5%. Maybe we did some calculation errors. 1st [CO3-2] =3.04*10-3 eq/L The error is more than 5%. Maybe we did some calculation errors. 2- ) A pH can be measured colorimetrically or electrometrically. The colorimetric methods are susceptible to interferences from turbidity, salinity, oxidants and colloidal matter. The color standards fade over time. The indicator solutions cover narrow portions of the pH scale requiring several sets of standards and indicators. For quick, general determination of a solutions pH, strips of specially impregnated paper are often used. These indicator strips change color when a certain pH level is reached. Phenolphthalein is a common indicator that is colorless in solutions below 8.3 SU and bright pink-red when greater than 8.3 SUpH. These strips are available in wide variety of formulations to provide useful versatility aids for the analyst. Modern determination of pH relies upon pH meters. The electrometric method is quite accurate and is the most commonly used. The electrode response must be calibrated each day and sometimes for each sample. The manufacturers directions should always be consulted for specific calibration instructions. The most correct calibration procedure is to choose buffer standards which bracket the suspected pH of the sample. The pH strips are quite useful in this situation. Corroboration and reliability checks validate the analysis when using completely different ways to arrive at the same number. Or, show a problem exists in the test equipment. Read what is there, not what you think is there or want to see. (pH and Alkalinity,para.12) 3- ) Chemical coagulation Chemicals used for coagulation of water and wastewater react with water to form insoluble hydroxide precipitates. The hydrogen ions released react with the alkalinity of the water. Thus, the alkalinity acts to buffer the water in a pH range where the coagulant can be effective. Alkalinity must be present in excess of that destroyed by the acid released by the coagulant for effective and complete coagulation to occur. (Insoluble hydroxide precipitates jar test dosage determination); Water softening (Alkalinity must be considered in calculating the lime and soda-ash requirements in softening of water by precipitation methods); the alkalinity of softened water is a consideration in terms of whether such waters meet drinking water standards. Corrosion Control Alkalinity is an important parameter involved in corrosion control. It must be known in order to calculate the Langelier saturation index. Buffer Capacity Alkalinity measurements are made as a means of evaluating the buffering capacity of wastewaters and sludges. They can also be used to assess natural waters ability to resist the effects of acid rain. Industrial Wastes Many regulatory agencies prohibit the discharge of wastes containing caustic (hydroxide) alkalinity to receiving waters. Municipal authorities usually prohibit the discharge of wastes containing caustic alkalinity to sewers. Alkalinity as well as pH is an important factor in determining the amenability of wastewaters to biological 3rd [CO3-2] =2.6*10-3 M (=5.2*10-3 eq/L) 3rd [HCO3-] =8.7*10-4 M (=8.7*10-3 eq/L)

treatment.(Cvl407-Lab6- Alkalinity,p.4) 6. REFERENCES: 1. University of Rhode Island, 2004.PH and Alkalinity web page: http:/www.uri.edu 2.Sawyer ,C.N., McCarty, P.L., Parkin , G.F., Chemistry for Environmental Engineering and Science 5th edition, The McGraw Hill Companies, New York, 2003 pp. 550-558 3. Snceyink, V.L., Jenkins, D., Water Chemistry, John Wiley & Sons, Inc., New York, 1980 pp. 173-183 4. CIVL407-Lab6-ALKALINITY-1.doc , retrieved 15 October www.civil.ubc.ca/home/env_lab/CIVL407-Lab6-ALKALINITY-1 2012 from,

5.pH and Alkalinity,retrieved 15 October 2012 from, http://home.windstream.net/mikeric/chap10up/Chapter%2012%20%20pH%20and%20Alk alinity.htm