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

Monroe L. Weber-Shirk

School of Civil and


Environmental Engineering

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

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Porous reference junction


Glass bulb (insulator) with
anionic sites

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Reference Voltage +
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pH 4 solution (high H+)
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Voltage across glass membrane


Solution voltage is 180 mV higher than reference!
We need a way to measure the solution voltage

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Glass membrane (Insulator)

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


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

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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 E0

E E0

RT FH

lnG
nF G
HH

I
JJ
K
RT ln(10) FH

logG
G
nF
HH

H + Reference (known) [H+]

I
JJ
K

RT ln(10)
0

E =E +
pH
- pH

nF
E E ) nF
(

pH pH 0

RT ln(10)

Faraday constant

Gas constant

E0

H
Voltage at

J
R 8.314
mol K
Coulombs
F 96500
mol e
n 1 mol e

Nernst Equation

E (mV)

pH pH 0

0
E

E
(
) nF

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

RT ln(10)

250
200
150
100
50
0
-50
-100
-150
-200
-250

J
R 8.314
mol K

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

Coulombs
F 96500
mol e
n 1 mol e

7
pH

10

Slope vs. Temperature

mV/pH

E 0.000198T pH 7
75
70
65
60
55
50
0

50

100

Temperature (C)

Temperature

compensation is important!

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

Buffer pH

Current measurement (E, T)

pH

Calibration Cases
0 or 1 standards w/ Temperature
nF E 0 E
0
pH

pH

R ln(10) T 0 T
ideal

pH =k pH

E
E
0
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pH

T 0 T

pH k ideal
pH

E
7
T

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

ideal

k pH

ideal

k pH

nF

R ln(10)

K
5040.8
Volt

No standards (assume ideal


slope and intercept)
Single standard (assume
ideal slope)

Multiple Point Calibrations w/


Temperature Compensation
How

would you use


this information to
calculate pH?

Calculate E/T
Piecewise linear fit

E (mV)

T (C)

Buffer
pH

23

185

24

-170

20

10

Current measurement (E, T)

pH