Theory Basics PH and Conductivity

Theory Basics: pH & Conductivity
Yvonne Y. Hou
KL, Malaysia
July 1 2009
Agenda
Principle of pH measurement
Principle of conductivity measurement
1 Internal usage only
Why do we measure pH ?
to produce products with defined properties
to produce products with less costs
to avoid damage to people, materials and environment
to fulfill regulatory requirements
to protect equipment
to get new knowledge, for research and development
Internal usage only
1
Where do we measure the pH value?
Environment and water utilities
Tap water
Industrial water
- Cooling / Heating
- Production processes
Waste water
Chemical processes
Swimming pools
Nuclear power plants
Food and beverages industries
Pharmaceutical and cosmetic industry
What is pH?
Definition pH
Electrode calibration (adjustment)
Temperature compensation
What is pH ?
pH
Its a measured value which indicates the degree of acidity of
an aqueous solution
2
pH measuring range: 0 - 14
Food & Beverages / Household products
Orange juice
Egg white
Cola
Cheese Water Antacida ( Mg(OH)2 )
Lemon juice
Beer Milk
Borax
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Caustic
Hydrochloric acid
Hydrocyanic acid soda 4%
0.37% (0.1 M) Calcium
0.27% (0.1 M) carbonate (sat)
Sulfuric acid Acetic acid Ammonia sol.1.7% (1 M)
4.9 % (1 M) 0.6% (0.1 M)
Ammonia sol. 0.017% (0.01 M)
Potassium acetate 0.98% (0.1 M)
Chemicals Sodium hydrogen carbonate 0.84% (0.1 M)
Why is it acidic ?
Acid is .
. bitter
. unpleasant
. (almost) inedible / undrinkable
Acids dissociate in water and release hydrogen ions H+:

HCl H+ + Cl- Hydrochloric acid
H2SO4 2 H+ + SO42- Sulfuric acid
HNO3 H+ + NO3- Nitric acid
CH3COOH H+ + CH3COO- Acetic acid
The degree of acidity is due to the presence of H+-ions

Why is something alkaline?
Base (alkali) is.

. caustic
. feels like soap water
A base dissociates in water and release hydroxide ions OH- :
NaOH Na+ + OH- Caustic soda
NH3 + H2O NH4+ + OH- Ammonia
CO32- + H2O HCO3- + OH- Carbonate
The degree of alkalinity is due to the presence of OH--ions
3
What is pH?
Definition pH
Definition of pH
A pH value is defined as:
the negative logarithm of the hydrogen ion concentration (cH+)
pH = - log cH+
Of any number in the format 10x, its logarithm is x
So for the concentration of H+ ions this means:
0.1 mol/l = 10-1 mol/l pH = 1

0.01 mol/l = 10-2 mol/l pH = 2
0.001 mol/l = 10-3 mol/l pH = 3
Definition of pH
The pH scale is determined by the dissociation of water, H2O:

H2O = H+ + OH
The product of the concentrations of these ions is constant:
cH+ * cOH- = 10-14 (25oC)
Range pH H+ concentration OH- concentration
(mol/L) (mol/L)
0 1 0.00000000000001
1 0.1 0.0000000000001
e=Z=J=xeHz acid
2 0.01
3 0.001
0.000000000001
0.00000000001
4 0.0001 0.0000000001
5 0.00001 0.000000001
6 0.000001 0.00000001
neutral 7 0.0000001 0.0000001
8 0.00000001 0.000001
9 0.000000001 0.00001
10 0.0000000001 0.0001
alkaline 11 0.00000000001 0.001
12 0.000000000001 0.01
13 0.0000000000001 0.1
14 0.00000000000001 1
Internal usage only
4
What is pH?
Definition pH
The pH is measured by potentiometry
glass reference
The measuring system consists of: electrode electrode
pH glass electrode pH Meter
reference electrode
The potential difference (mV) is measured:
E = EGlass - EReference
Nernst equation
E = Eo + 2.3 RT/F log cH+
E = Eo 2.3 RT/F pH
E Measured potential mV
Eo Standard potential
R Universal gas constant pH
T Temperature (Kelvin)
1 7 14
F Faraday constant
2,3 RT/F Nernst potential (slope)
cH+ H+ concentration of solution
Potential difference of 1 pH unit = 59.16 mV (at 25 C)

5
What is pH?
Definition pH
Accuracy of pH measurement
What does the accuracy of pH measurement depend on?

Calibration
- correct and frequent procedure
- new and accurate buffers
Temperature
- differences between calibration and measurement
- temperature measurement and control
Electrode
- correct type (correct membrane glass)
- clean diaphragm
Realistic accuracy in the laboratory: 0.05 pH
Adjustment
1. Offset adjustment
Buffer pH 7.00
mV
After adjustment:
Offset = -10 mV
Before adjustment:
(calibration)
pH
4 7 9
Offset = 0 mV (ideally)
6
Adjustment
2. Slope adjustment
Buffer pH 4.01
mV
Before adjustment:
(calibration)
pH
4 7 9
After adjustment
Slope = -58.9 mV/pH
Adjustment
Conditions
Always use fresh buffers.

- Use the same buffer solution only once,
- Otherwise there is no guarantee for the
correct value of the buffer solution.
Clean the electrode after the measurement.
Measure the temperature.

- All METTLER TOLEDO pH meters and
titrators have an automatic temperature
compensation.
What is pH?
Definition pH
7
What is the temperature compensation in a pH meter?
According to the Nernsts law the slope of the electrode is temperature dependent:
oC mV/pH
E = Eo - 2,3 RT/F pH 0 -54.2
10 -56.2
mV 20 -58.2
25 -59.2
30 -60.1
40 -62.1
50 -64.1
pH 60 -66.1
20 oC 80 -70.1
7 90 -72.1
25 oC
100 -74.0
110 -76.0
40 oC
The T-compensation in a pH meter doesnt compensate for:
pH value of a solution at different temperature
Samples 20C 30C

HCl 0.001 mol/L pH 3.00 pH 3.00
NaOH 0.001 mol/L pH 11.17 pH 10.83
Phosphate buffer pH 7.43 pH 7.40
TRIS buffer pH 7.84 pH 7.56
Each solution has its own temperature dependence!

It is NOT possible to compensate for this effect with a pH meter.
Always measure the temperature with each pH measurement

Temperature Compensation
What does the pH meter compensate for?
The pH meter or titrator has a temperature compensation for the slope of
the electrode
There is no compensation for the temperature dependence of the pH

value of the sample itself
Exception: Standard buffers; the temperature dependence of the buffers

(METTLER TOLEDO, MERCK, etc.) are stored in the pH meters and
titrators.
8
Agenda
Applications
fresh water monitoring

checking purity of deionized water.
swimming pools
checking natural streams
industrial heating/cooling
effluent streams in industry
food & beverage industry
pharmaceutical industry
desalination plants
power plants
chemical processes
acid-base concentration determination
What is conductivity
The theory
The cell constant and the sensors
Low conductivity measurements
Calibration / Sensor adjustment
Other conductivity units
- Concentration
- TDS (total dissolved solids)
- Salinity
- Resistivity
9
What is conductivity?
Conductivity is
the ability of a solution to pass current.
The amount of current flowing:

is proportional to the number of ions
present in the solution.
As more ions, as higher the conductivity!
Conductivity measurement gives

information about:
- total content of all ions in a solution.
- the ion concentration in the solution
The theory
- Concentration
- Salinity
- Resistivity
The theory
Conductivity measurement
An alternating voltage is applied across
two plates.
In the sample solution, the voltage
induces a current. Current Source
The ions move towards plates.
Voltage
This current* between the plates is - +
measured.
This gives a direct value for the conductivity - +
of the solution.
U=RI
- + +
-
+ +
U = Voltage [mV]
R = Resistance [Ohm]
I = Current [mA]
Ionic mobility in a solution
* For measurement, AC current is converted to DC to give the actual reading.
10
The theory
Faradays Law Michael Faraday

1791 - 1867
England
C=GL/A
C = conductivity [ S/cm or mS/cm] Current Source
G = conductance [S or mS]
Voltage
G=I/U =1/R - +
U = Voltage [mV]
R = Resistance [Ohm]
- +
I = Current [mA] - + +
-
+ +
Z=L/A
Z = cell constant of the electrodes [cm-1]
L = distance between electrodes [cm] Ionic mobility in a solution
A = plate area of the electrodes [cm2]
The theory
- Concentration
- Salinity
- Resistivity

J H
Cell constant
The cell constant Z of the sensor is defined by Z = L/A
- Distance between the plates =L N
- Area of the plates =A
Each conductivity sensor has its own cell constant! ^ZN O
N
iZN
Standard cell Surface 1 cm2
1 cm
- Cell constant Z = L / A = 1.0/cm
For high conductivity

For low conductivity

11
Sensor application
0.1 1.0 10 100 1000 S/cm

Water extra pure 1 10 100 1000 mS/cm
Tap water Waste water

Deion water Sea water
Conc. acid & base
Cell constant 0.1 / cm
Cell constant 10 / cm
error
10 %
5%
0%
-5%
- 10 %
METTLER TOLEDO Conductivity sensors
SevenEasy S30 and SevenMulti S70 Conductivity

InLab710 cc 0.80/cm 10 S/cm 500 mS/cm
InLab720 cc 0.06/cm 0.1 S/cm 500 S/cm
InLab731 cc 0.57/cm 10 S/cm 1000 mS/cm
InLab741 cc 0.105/cm 0.001 S/cm 500 S/cm
SevenGo (Duo)
InLab738 (IP67) cc 0.57/cm 0.05 mS/cm 1000 mS/cm
InLab742 (IP67) cc 0.105/cm 0.001 S/cm 500 S/cm
- InLab710, InLab720, InLab731 and InLab741 with special adapter
Conductimetric titration
InLab717 cc undefined higher conductivity
InLab718 cc undefined 0.1 to 200 S, non-aqueous
>
The theory
- Concentration
- Salinity
- Resistivity
12
Low Conductivity Measurement
Flow through cell
Sensor with a small cell constant

InLab741
Flow through cell
Low Conductivity Measurement
Conductivity and pH measurement

Influence of the KCl flow (electrolyte leak) of the pH electrode
DGi111 (KCl 3 mol/L) 1 mL KCl/24 h

DGi114 (KCl 3 mol/L) 3 mL KCl/24 h
Time DGi111 DGi114

30 s 4 S/cm 10 S/cm
1 min 6 S/cm 18 S/cm
KCl 3 min 18 S/cm 55 S/cm
Low conductivity: separate measurement of pH and conductivity!
The theory
- Concentration
- Salinity
- Resistivity
13
Calibration/ Sensor Adjustment
Sensor adjustment = Determination of the cell constant
One point adjustment with conductivity standard: 84 S/cm

Zero point (0 S/cm) automatic 1413 S/cm
12.88 mS/cm
Or enter cell constant manually
SEVEN Easy SEVEN Multi
Also with user defined standards possible.

Extra 10 and 500 S/cm standards.
More than one calibration point.
Calibration/ Sensor Adjustment
Tips & Hints
SEVEN Easy SEVEN Multi
Always use fresh standard

Cleaning: Rinse the probe and dab dry between measurements
InLab741/742: certificate with accurate cell constant
Question:
Enter cell constant from certificate or do an adjustment?
Which is the optimum procedure?
The theory
- Concentration
- Salinity
- Resistivity
14
Conductivity: Temperature effects
` `
Conductivity is temperature dependent
The conductivity of a solution will increase with temperature.

Conductivity change as a function of T
- Expressed by , the % change of conductivity per C
Temperature dependence is
- Different for each different solution
- Can vary with concentration.
Substance Concentration T-coeff. Concentration T - coeff

at 25 oC % %
HCl 0.5 1.4 10 1.56

KCl 0.8 1.9 10 1.88
NaCl 10 2.14
HF 1.5 7.20

` `
Conductivity is temperature dependent
The conductivity of a solution will increase with temperature.
Conductivity temperature coefficient
Expressed by value, Concentration Conductivity
Temp
Substance coefficient
the % change of conductivity per C wt% mS/cm
%/C
5 395 1.58
10 630 1.56
Temperature dependence is 20 762 1.54
- Different for each different solution. 6.2 312 1.47
12.4 542 1.42
- Can vary with concentration. 31.0 782 1.39
5 209 1.21
10 392 1.28
20 653 1.45
10 1.53 1.69
15 1.62 1.74
20 1.61 1.79
5 69 2.01
10 136 1.88
15 202 1.79
5 67 2.17
10 121 2.14
15 164 2.12

` `
Reference temperature: 20 oC or 25 oC
To compare measurements made at different temperatures:

MUST reference to a standard temperature 20 oC or 25 oC.
Example: Measure conductivity at 30C
Result on display: Conductivity is at the
reference temperature (20 C or 25 C)
The conductivity meter calculates the conductivity at reference temperature (20C or 25
C) using the temperature coefficient alpha (% / C)
= Temperature compensation
A correct determination of the temperature coefficient alpha (% / C) of this

sample is needed.
15
Determination of the alpha value (% / C)

Measure the conductivity of a solution at two different temperatures
WITHOUT temperature compensation (alpha value = 0.0)
Conductivity (S/cm)
CT1 - CTref
CTref
CTref = 100%
T1 Tref
CT1
= T-coefficient of the solution at Tref [%/C]
CT1 = conductivity at T1
CTref = conductivity at Tref
T1 Tref T (C) T1 = measuring temperature 1 [C]
Tref = reference temp. 20 or 25 [C]
Check of the alpha value (% / C)

Measure conductivity at different temperature: 30 and 35 C
If the conductivity measurement of a sample at two different
temperatures doesnt give the same value, the alpha value is wrong.
conductivity
alpha value correct
alpha value to low
alpha value = 0
alpha value too high
temperature
25 30 35
Nonlinear temperature dependence

Over a large temperature range, the temperature dependence is non-linear !
conductivity
real
linear
10 50 temperature
The alpha value is not constant over whole temperature range !
16
Automatic temperature compensation
Temperature compensation in conductivity

has NOT the same meaning as in pH meas.
Conductivity measurement temperature dependence of sample
- A reference temperature of e.g. 25C is defined
- The conductivity of a sample at e.g. 30C is measured
- Result: Conductivity value which would be at 25C, using alpha value.
pH measurement temperature dependence of electrode

- Temp. compensation is active in the pH meter (T-probe is connected)
- The pH value of the sample is measured at 30C
- Result: pH value of the sample at 30 C using adjustment line at 30C
+ mV
pH
20 oC
7
25 oC
- mV 30 oC
The theory
- Concentration
- Salinity
- Resistivity
TDS (total dissolved solids)

- TDS is a measurement of ion concentration (mg/L or ppm).
- TDS factor = TDS / conductivity (mS/cm).
When working with TDS, select the appropriate TDS factor (0.40-1.00).
- This conversion factor allows to give a TDS value referred to a calibration
standard (usually KCl, NaCl or CaCO3).
Salinity
- Ratio of salt in a sample to salt in seawater (NaCl)
U = Voltage [mV]
Resistivity G=I/U =1/R R = Resistance [Ohm]
I = Current [mA]
- Resistivity is the reciprocal of conductivity
- Raw data of conductivity measurement (ohm cm)
- Resistivity is common in industries where ultra pure water is required.
17
Conductivity at higher ion concentrations
Concentration linearity
Over a bigger concentration range there is no linear dependence between
conductivity and concentration.
Summary
Conductivity is a measure of the total ion concentration
Conductivity depends on
- The nature of the solution
- The nature of the ions
- The concentration of ions
- The temperature
Accurate results can be achieved by

- measuring standards and samples at the same temperature.
Thank you!
Source: XXX 53 Internal usage only
18

Theory Basics PH and Conductivity

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Theory Basics: pH & Conductivity

1 Internal usage only

to produce products with less costs

to avoid damage to people, materials and environment

to fulfill regulatory requirements

to get new knowledge, for research and development

Internal usage only

Nuclear power plants

Food and beverages industries

Pharmaceutical and cosmetic industry

3 Internal usage only

4 Internal usage only

5 Internal usage only

Chemicals Sodium hydrogen carbonate 0.84% (0.1 M)

6 Internal usage only

Acids dissociate in water and release hydrogen ions H+:

HNO3 H+ + NO3- Nitric acid

CH3COOH H+ + CH3COO- Acetic acid

The degree of acidity is due to the presence of H+-ions

Why is something alkaline?

Base (alkali) is.

A base dissociates in water and release hydroxide ions OH- :

NaOH Na+ + OH- Caustic soda

NH3 + H2O NH4+ + OH- Ammonia

CO32- + H2O HCO3- + OH- Carbonate

The degree of alkalinity is due to the presence of OH--ions

8 Internal usage only

9 Internal usage only

A pH value is defined as:

the negative logarithm of the hydrogen ion concentration (cH+)

Of any number in the format 10x, its logarithm is x

So for the concentration of H+ ions this means:

0.1 mol/l = 10-1 mol/l pH = 1

10 Internal usage only

12 Internal usage only

The potential difference (mV) is measured:

13 Internal usage only

Potential difference of 1 pH unit = 59.16 mV (at 25 C)

15 Internal usage only

What does the accuracy of pH measurement depend on?

Realistic accuracy in the laboratory: 0.05 pH

16 Internal usage only

17 Internal usage only

Slope = -58.9 mV/pH

18 Internal usage only

Always use fresh buffers.

Clean the electrode after the measurement.

Measure the temperature.

19 Internal usage only

20 Internal usage only

21 Internal usage only

pH value of a solution at different temperature

Samples 20C 30C

Each solution has its own temperature dependence!

Always measure the temperature with each pH measurement

There is no compensation for the temperature dependence of the pH

Exception: Standard buffers; the temperature dependence of the buffers

23 Internal usage only

24 Internal usage only

fresh water monitoring

25 Internal usage only

Principle of conductivity measurement

26 Internal usage only

The amount of current flowing: