EXPERIMENT Calibration of pH meter Determination of pH at different temperatures APPARATUS & CHEMICALS Digital pH meter Heater Beaker Acid solution

Thermo meter Teflon coated stirring bar Magnetic stirrer Buffer Solutions (pH-4&7) Combination pH electrode (or a glass electrode coupled with a standard reference electrode) INTRODUCTION The pH probe measures pH as the activity of hydrogen cations surrounding a thin-walled glass bulb at its tip. The probe produces a small voltage (about 0.06 volt per pH unit) that is measured and displayed as pH units by the meter. It use all ph testing, water purification application, waste water regulation, aquaculture, hydroponics, colloidal silver, pools &saps, ecology testing, water treatment, industry and etc. pH can be viewed as an abbreviation for power of Hydrogen - or more completely, power of the concentration of the Hydrogen ion.The mathematical definition of pH is a bit less intuitive but in general more useful. It says that the pH is equal to the negative logarithmic value of the Hydrogen ion (H+ or H3O+) concentration, pH = -log [H+] pH values are calculated in powers of 10. The hydrogen ion concentration of a solution with pH 1.0 is 10 times larger than the hydrogen concentration in a solution with pH 2.0. The larger the hydrogen ion concentration, the smaller the pH.

when the pH is above 7 the solution is basic (alkaline)

when the pH is below 7 the solution is acidic

In pure neutral water the concentration of hydrogen and hydroxide ions are both 10-7 equivalents per liter. PROCEDURE Calibration should be performed with at least two standard buffer solutions that span the range of pH values to be measured. For general purposes buffers at pH 4 and pH 10 are acceptable. The pH meter has one control (calibrate) to set the meter reading equal to the value of the first standard buffer and a second control (slope) which is used to adjust the meter reading to the value of the second buffer. A third control allows the temperature to be set. Standard buffer sachets, which can be obtained from a variety of suppliers, usually state how the buffer value changes with temperature. For more precise measurements, a three buffer solution calibration is preferred. As pH 7 is essentially, a "zero point" calibration (akin to zeroing or tarring a scale or balance), calibrating at pH 7 first, calibrating at the pH closest to the point of interest ( e.g. either 4 or 10) second and checking the third point will provide a more linear accuracy to what is essentially a non-linear problem. Some meters will allow a three point calibration and that is the preferred scheme for the most accurate work. Higher quality meters will have a provision to account for temperature coefficient correction, and high-end pH probes have temperature probes built in. The calibration process correlates the voltage produced by the probe (approximately 0.06 volts per pH unit) with the pH scale. After each single measurement, the probe is rinsed with distilled water or deionized water to remove any traces of the solution being measured, blotted with a scientific wipe to absorb any remaining water which could dilute the sample and thus alter the reading, and then quickly immersed in another solution.

Buffers - reference values

A pH meter calibration is performed by measuring a series of reference standards, so-called pH buffers that have known and accurate pH values at different temperatures.

The main steps for a generic pH calibration procedure: 1) Turn the pH meter on and allow adequate time to warm up (check the operating manual).

2) Select two pH buffers that bracket the expected sample pH. The first buffer should be pH 7.00 (zero point adjustment) and the second buffer should be near the expected sample pH (pH 4 or pH 9.21). If you will measure both acidic and basic samples, and only perform one pH calibration, you should use a multi-point calibration.

3) Before starting calibration, be sure the sensor and the buffer solution are at the same temperature. If not, allow time for temperature equilibration.

4) Pour the necessary amount of buffer solutions into individual glass beakers. Buffer solutions will remain stable in a glass beaker for a maximum of 2 hours. Note: To minimize the risk of contamination, calibrations should never be carried out in the storage container.

Close the buffer containers promptly to avoid carbon dioxide absorption. Do not pour used buffer back into the storage container. Discard it.

5) Place the electrode into the first buffer. When the reading is stable, set the pH meter to the pH value of the first buffer at the measured temperature. Most modern pH meters have an "autoread" function for early detection of a stabilized reading.

It is not strictly necessary to stir samples for pH measurement. However, if the buffer solutions are stirred, then the sample should also be stirred in the same way.

6) Between buffers, rinse the electrode with distilled water and then with the next buffer.

If you, for some reason, not want to rinse the pH electrode with the next buffer; Rinse the electrode with distilled water and gently blot it dry with a lint-free tissue. Avoid rubbing or wiping the electrode bulb.

7) Repeat step 3 for the next buffer. 8) When the pH meter calibration is done, rinse the electrode and place into the sample and make our pH measurement.

Calibration Verification 1. Use the same buffers that were used for calibration or prepare fresh buffers as described in the Calibration Buffer Preparation section. Uncover the calibration verification beakers. 2. Rinse the pH electrode first with deionized water and then in the pH 10.01 buffer rinse beaker. Make sure to rinse the electrode with deionized water over a waste beaker to prevent contamination of the buffers. The electrode should never be rinsed in the same buffer beaker that will be used for calibration verification. 3. Place the electrode into the pH 10.01 buffer calibration verification beaker, so the electrode tip and junction are fully immersed in the buffer, and stir the buffer at a moderate, uniform rate. 4. Start the measurement on the meter. 5. Wait for a stable reading, at least 1 to 2 minutes, and then record the pH and temperature of the buffer. 6. Repeat steps 2 through 5 for the pH 7.00 buffer and then the pH 4.01 buffer. 7. Compare the recorded pH and temperature values of the buffers to those listed in Table 1 on the right. 8. Rinse the pH electrode with deionized water and store the electrode in pH electrode storage solution until the samples are ready for measurement.

OBSERVATION: Temperature -25 0C Solution1-pH 7 Solution11-pH 4.01

Temperature 35 45 55 65 Acid pH 4.87 Alkali pH 10.93

pH value

Conclusion When the temperature of solution is increased, the activity & concentration of H3O+ increases in the solution. So the pH value decreases. (pH = -log [H+] is true) Discussion pH meters measure the H+ concentration (the pH) of solutions using an ion sensitive electrode. An ion-selective electrode will ideally respond to only one specific ion, though in reality there is always some degree of interference from other ions in solution. A typical modern pH probe is a combination electrode, which combines both the glass and reference electrodes into one body. The bottom of a pH electrode balloons out into a round thin glass bulb. The pH meter is best thought of as a tube within a tube. The inside most tube (the inner tube) contains an unchanging saturated KCl and a 0.1M HCl solution. Also inside the inner tube is the cathode terminus of the reference probe. The anodic terminus wraps itself around the outside of the inner tube and ends with the same sort of reference probe as was on the inside of the inner tube. Both the inner tube

and the outer tube contain a reference solution but only the outer tube has contact with the solution on the outside of the pH probe by way of a porous plug that serves as a salt bridge. This device is essentially a galvanic cell. The reference end is essentially the inner tube of the pH meter, which for obvious reasons cannot lose ions to the surrounding environment (as a reference is good only so long as it stays static through the duration of the measurement). The outer tube contains the medium, which is allowed to mix with the outside environment (and as a consequence this tube must be replenished with a solution of KCl due to ion loss and evaporation). The measuring part of the pH meter, the glass bulb on the bottom, is coated both inside and out with a 10nm layer of a hydrated gel. These two layers are separated by a 0.1mm layer of dry glass. The silica glass structure (that is, the conformation of its atomic structure) is shaped in such a way that it allows Na+ions some mobility. The metal cations (Na+) in the hydrated gel diffuse out of the glass and into solution while H+ from solution can diffuse into the hydrated gel. It is the hydrated gel, which makes the pH electrode an ion selective electrode. H+ does not cross through the glass membrane of the pH electrode, it is the Na+ which crosses and allows for a change in free energy. When an ion diffuses from a region of activity to another region of activity, there is a free energy change and this is what the pH meter actually measures. The hydrated gel membrane is connected by Na+ transport and thus the concentration of H+ on the outside of the membrane is 'relayed' to the inside of the membrane by Na+.

When one metal is brought in contact with another, a voltage difference occurs due to their differences in electron mobility. When a metal is brought in contact with a solution of salts or acids, a similar electric potential is caused, which has led to the invention of batteries. Similarly, an electric potential develops when one liquid is brought in contact with another one, but a membrane is needed to keep such liquids apart. A pH meter measures essentially the electro-chemical potential between a known liquid inside the glass electrode (membrane) and an unknown liquid outside. Because the thin glass bulb allows mainly the agile and small hydrogen ions to interact with the glass, the glass electrode

measures the electro-chemical potential of hydrogen ions or the potential of hydrogen. To complete the electrical circuit, also a reference electrode is needed. Note that the instrument does not measure a current but only an electrical voltage, yet a small leakage of ions from the reference electrode is needed, forming a conducting bridge to the glass electrode. A pH meter must thus not be used in moving liquids of low conductivity (thus measuring inside small containers is preferable).

The pH meter measures the electrical potential (follow the drawing clock-wise from the meter) between the mercuric chloride of the reference electrode and its potassium chloride liquid, the unknown liquid, the solution inside the glass electrode, and the potential between that solution and the silver electrode. But only the potential between the unknown liquid and the solution inside the glass electrode change from sample to sample. So all other potentials can be calibrated out of the equation. The calomel reference electrode consists of a glass tube with a potassium chloride (KCl) electrolyte which is in intimate contact with a mercuric chloride element at the end of a KCL element. It is a fragile construction, joined by a liquid junction tip made of porous ceramic or similar material. This kind of electrode is not easily 'poisoned' by heavy metals and sodium. The glass electrode consists of a sturdy glass tube with a thin glass bulb welded to it. Inside is a known solution of potassium chloride (KCl) buffered at a pH of 7.0. A silver electrode with a silver chloride tip makes contact with the inside solution. To minimise electronic interference, the probe is shielded by a foil shield, often found inside the glass electrode. Most modern pH meters also have a thermistor temperature probe which allows for automatic temperature correction, since pH varies somewhat with temperature.

Caring for a pH meter depends on the types of electrode in use. Study the manufacturer's recommendations. When used frequently, it is better to keep the electrode moist, since moisturising a dry electrode takes a long time, accompanied by signal drift. However, modern pH meters do not mind their electrodes drying out provided they have been rinsed thoroughly in tap water or potassium chloride. When on expedition, measuring sea water, the pH meter can be left moist with sea water. However for prolonged periods, it is recommended to moist it with a solution of potassium chloride at pH=4 or in the pH=4.01 acidic calibration buffer. pH meters do not like to be left in distilled water.