V

+ +

pH measurements
The probe, from chemistry to voltage to a number

pH probe
V Buffered KCl solution 4 M KCl solution Reference electrode Silver/silver chloride electrode Sensing electrode
+ + + + + + + + + ++ + + + + + + + + + + + + ++ + + ++ + +

++ + + + ++ + ++ + + + + + + ++ + + + + + + + + + + ++ + + + + + ++ + + + + +

+ + + +

Porous reference junction

Glass bulb (insulator) with anionic sites

Glass membrane (Insulator)

+ + + + + + + + + + + + + + +

Voltage across glass membrane Solution voltage is 180 mV higher than reference!

+ + + + + + + + + + + + + + + + + + + + + + + + + + + + ++ + + + + + + +

+ + + + + + + + + + + + + + + + + ++ + + + + + + + + + + + + + + + + + + + Reference Voltage + + + + + + + + Call it zero! + + + + + + + + + ++ + + + + ++ ++ ++ + + + +++ + + ++ ++++++ + + + + ++ + + + + + + pH 4 solution (high H+) + +

+ + + + + + + + +

+ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +

pH Measurements
The porous frit provides electrical contact between the solution and the electrolyte
Must be in contact with the sample solution Probe wont work well if frit is clogged (fouled)

+ +

The voltage measurement requires a very high __________ circuit (high resistance) impedance because a pH probe cant produce much current Gentle stirring keeps the solution next to the glass bulb from being depleted of protons

Difficult Measurements?
pH is difficult to measure in poorly buffered solutions
Distilled water Rain Between pKs of dilute buffers

Nernst Equation: Voltage = f(pH)

E E 0

E E 0

I J J K H RT ln(10) F logG G nF H H

H RT F lnG nF G H H

H + Reference (known) [H+]

0

I J J K

E0

H + Voltage at
0

F R

Faraday constant
Gas constant
J R 8.314 mol K Coulombs F 96500 mol e

RT ln(10) pH 0 - pH E=E + nF
0

pH = pH 0

(E - E ) nF 0

RT ln(10)

n 1 mol e

Nernst Equation
pH = pH 0 250 200 150 100 50 0 -50 -100 -150 -200 -250 4 5 6 7 pH 8

E - E 0 ) nF ( RT ln(10)

0 E nF E pH = pH + 0 - T T R ln(10)
0

E (mV)

E at 0 C E at 25 C E at 35 C E at 100 C

J R 8.314 mol K
Coulombs F 96500 mol e

n 1 mol e
9 10

Slope vs. Temperature

E 000198T pH 0. 7
75 70 65 60 55 50 0 50 Temperature (C) 100
mV/pH

Temperature compensation is important when temperature changes between

pH Calibration
It would be possible to make a pH measurement without any calibration
Based on theoretical values This is how the software recognizes buffers!

Calibration accounts for non-ideal probe behavior (fouling) as well as electronic measurement errors It is important that buffers be used covering the range of pH measurements

The Challenge
0 to 3 known buffers used as standards Temperature compensation optional E T Buffer pH

pH

Current measurement (E, T)

Calibration Cases 0 or 1 standards w/ Temperature

nF 0 E E pH = - + pH 0 R ln(10) T 0 T pH = k pH
ideal

k pH

ideal

nF = R ln(10)

E E - + pH 0 T 0 T
0

k pH

ideal

K = 5040.8 Volt

pH = - k ideal pH

E +7 T

No standards (assume ideal slope and intercept) Single standard (assume ideal slope)

1 E ideal E pH = k pH 1 - + pH 1 T T

Multiple Point Calibrations w/ Temperature Compensation

How would you use this information to calculate pH?
Calculate E/T Piecewise linear fit
E (mV) 8 185 -170 T (C) 23 24 20 Buffer pH 7 4 10

pH

Current measurement (E, T)

pH
pH is a unit of measure which describes the degree of acidity or alkalinity (basic) of a solution. It is measured on a scale of 0 to 14. The formal definition of pH is the negative logarithm of the hydrogen ion activity. pH = -log[H+]

pH value
The pH value of a substance is directly related to the ratio of the hydrogen ion and hydroxyl ion concentrations. If the H+ concentration is higher than OHthe material is acidic. If the OH- concentration is higher than H+ the material is basic. 7 is neutral, < is acidic, >7 is basic

The pH scale
The pH scale corresponds to the concentration of hydrogen ions. If you take the exponent of the H3O+ concentrations and remove the negative sign you have the pH of the solution. For example pure water H+ ion concentration is 1 x 10^-7 M, therefore the pH would then be 7.

pH
The addition of acid to water increases the concentration of hydrogen ions and reduces the concentration of hydroxyl ions The addition of a base would increase the concentration of hydroxyl ions and decrease the concentration of hydrogen ions

Acids and Bases

An acid can be defined as a proton donor, a chemical that increases the concentration of hydrogen ions in solution. A base can be defined as a proton acceptor, a chemical that reduces the concentration of hydrogen ions in solution.

pH Measurement
A pH measurement system consists of three parts: a pH measuring electrode, a reference electrode, and a high input meter. The pH measuring electrode is a hydrogen ion sensitive glass bulb. The reference electrode output does not vary with the activity of the hydrogen ion.

pH Meter
A sample is placed in a cup and the glass probe at the end of the retractable arm is placed in it. The probe is connected to the main box. There are two electrodes inside the probe that measure voltage. One is contained in liquid with fixed pH. The other measures the acidity of the sample through the amount of H+ ions.

pH Meter
A voltmeter in the probe measures the difference between the voltages of the two electrodes. The meter then translates the voltage difference into pH and displays it on the screen. Before taking a pH measurement the meter must be calibrated using a solution of known pH.

Temperature and Buffers

Temperature compensation is contained within the instrument because pH electrodes are temperature sensitive. Temperature compensation only corrects for the change in the output of the electrode, not for the change in the actual solution. Buffers are solutions that have constant pH values and the ability to resist changes in pH. They are used to calibrate the pH meter.