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Title:To calibrate pH meter and measure the pH of a provided sample.

Theory:
The pH scale is a series of numbers. These numbers express the degree of acidity or alkalinity of a solution. According to Sorensen pH is defined as negative logarithm(to the base 10) of molar hydrogen ion concentration. pH= log10 1/[H+] = -log10[H+], or [H+] = 10-pH Actually, it is the activity of hydrogen ion that is compatible with the thermodynamics. Hence activity definition of pH is: pH = -log10 aH+ = -log10 [H+].f H+ But being pragmatic, the ionic activity coefficient is assumed unity and therefore activities become equivalent to concentrations is an accepted simplification for our purpose. However pure the water is, it possesses a small but definite conductivity due to ionization: H2O H++ OHBy applying the law of mass action in the above equation: [H+][OH-] = Constant [ H2O] In pure water or dilute aqueous solution, [H2O] is a constant; hence [H+][OH-] = Kw Where, Kw is the ionic product of water( 1.008 X 10-14). In pure water or in neutral solution when the concentration of hydrogen and hydroxyl ions are equal: [H+] = [OH-] = Kw= 10-7(at 25C) or [H+][OH-] = Kw = 10-14 or log[H+] + log[OH-] = logKw= -14 Hence, pH + pOH = pKw = 14 For a neutral solution pH= pKw/2. Acid and alkaline solutions have pH values less and more than pKw/2. For pure water pH=7.0, for a solution with 1M hydrogen ion concentration pH=0 and for a solution with 1M hydroxide ion concentration pH= 14. H+= 10-010-110-210-310-410-510-610-710-810-910-1010-1110-1210-1310-14

pH= 0

7 8 9 10 11 12 13 14 Alkaline solution Neutral Only with the definition and mathematical explanations as above pH of a solution can not be measured. There are many methods are employed for the measurement of pH. The most accurate method is potentiometric determination of pH in which an indicatior electrode reversible to H+ is coupled with a reference electrode to form a cell. The emf of the cell varies with the hydrogen ion concentration of the solution in the cell.The emf of the cell is measure by potentiometer. If the other variables in the cell are controlled, the emf of the cell can be correlated with the pH and this correlation is the basis potentiometric measurement of pH. Hydrogen, quinhydrone, antimony-antimony oxide and glass electrodes are the indicator electrodes for the measurement of pH. However due to the existence of high resistance in glass electrode(which is nowadays in use) simple potentiometer is not applicable. Hence, the modern pH meter is an electronic digital voltmeter, scaled to read pH directly. Saturated calomel electrode is the most popularly used reference electrode. pH of an aqueous solution can be measured by coupling a glass electrode with a saturated calomel electrode. Outer connection is completed via a pH meter or potentiometer. The resulting cell can be represented as follows: HgHg2Cl2,KCl(satd.) H+(a=x) glass HCl(0.1M), AgClAg ______SCE________ _Test Soln_ _______Glass electrode_______

1 2 3 4 Acidic solution

5 6

In the above schematic cell diagram, a reference electrode is placed in each of the solutions separated by the glass membrane. So that, any change in the cell voltage when changed is made in the test solution must reflect a change in the potential developed across the glass membrane. Additionally, any change in the liquid junction potential between the SCE and the test solution be reflected. It is found experimentally that the voltage of this cell follows the relation at 25C over a pH range in the test solution from about 0 or 1 up to 10 or 13, depending upon the composition of the electrode. E = k+ 0.0592pH i.e. E/pH = 0.0592

A linear relation exists between the pH of a solution , at a given temperature and emf of cell(E). Thus, a calibration in mV may be converted into pH units by dividing by 0.0592. K is a constant which is lumped with asymmetry potential, liquid junction potential, standard potential of glass electrode, potential of reference electrode. To maintain uniformity in pH measuring technique and measured value of pH throughout the world, it is necessary to redefined pH in operational terms. According to the definition, first of all the meter is directly calibrated against standard buffers followed by potentiometric determination of the pH of unknown solution. Eu= k+ 0.0592 pHu or pHu = Eu- k ---------------(1) 0.0592 Es= k+ 0.0592 pHs or pHu = Es- k ---------------(2) 0.0592 Subtracting equation (2) from (1), pHu= pHs+ Eu Es 0.0592 According to this relation, pH of test solution is related to the difference between the emf due to standard buffer and test solution. With this operational definition liquid junction potential and asymmetry potential(which changes with time) are almost alleviated.

Chemicals required:
1)Standard buffer solution of 9.0,7.0 and 4.0, 2)Sodium chloride injection ,3)Ammonium chloride,4)ORS Sachets,5)Freshly boiled and cooled water.

Apparatus required:
1) Digital pH meter, 2)Beakers,3)Volumetric flasks .

Procedure:
Preparation of standard buffer solutions. Tranfer buffer tablets of pH 4.00 , 7.00 and 9.20 into different 100ml V.F. and shake to dissolve and dilute to the mark with boiled and cooled water. Maintain their temperature at 25C. Preparation of sample solution: a.Prepare 5.0%w/v solution of ammonium chloride in boiled and cooled water. pH limits: 4.5 6.0 b.Transfer a sachet full of ORS into a beaker(1L) containing about 900ml boiled and cooled water, stir to dissolve and dilute to the mark. pH limits:7.0-8.8 c.Sodium chloride injection. pH limits:4.5-7.0 Calibration of pH meter and measurement of pH of test solution:

1)Switch on and allow the instrument to warm up. Align the function switch to Stand by. 2)Wash the combination glass electrode with a small amount of buffer solution of pH 4.00 and dip it into the buffer in a small beaker. Measure the temperature of the solution and set the temperature control to this value. 3)Turn the function switch to pH. Adjust the Calibrate control until the meter reading agrees with the known pH of the buffer solution(25C) or temperature compensated buffer value. 4)Remove the electrode assembly and rinse in distilled water followed by second buffer and place into a small beaker containing a little of the second buffer(pH 7.00 or 9.20) solution. If the meter reading does not agree exactly with the known pH, adjust the Slope control until the required reading is obtained. 5.Remove the electrode assembly, rinse in distilled water, place in the first buffer solution and confirm that the correct pH reading is shown on the meter, if not, repeat the calibration procedure. 6.Following the completion of calibration, rinse the electrode with water followed by test solution and introduce into the test solution contained in a smaller beaker. Read off the pH of the solution. 7.Remove the electrode ,rinse in distilled water, and leave standing in distilled water.

Observations:
a. Ammonium chloride/ b.ORS/c.Sodium chloride injection, measured pH: