pH Theory

Applied to Proper Hardware

Selection

Feb 2001

File Name: pH.ppt

pH Theory
pH is a Unit of Measurement
pH = Power of Hydrogen (H+)
Defined as the Negative Logarithm of Hydrogen
Ion Activity
pH = log (1/H+)

Used for Determining the Acidity or Alkalinity

of an Aqueous Solution
Practical pH Scale for Industrial Instrumentation
0 - 14 pH

Feb 2001

File Name: pH.ppt

Acids and Bases

Acid dissolves in
water to furnish H+
ions

Feb 2001

Base dissolves in
water to furnish OHions

HCl H+ + ClHNO3 H+ + NO3-

NaOH Na+ + OH-

HF

NH4OH NH4+ + OH-

H+ + F-

File Name: pH.ppt

KOH

K+

+ OH-

Ion Concentration (mol/l)

Acid

Neutral

Alkaline

Feb 2001

pH
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14

Hydrogen Ion (H+)

1
0.1
0.01
0.001
0.0001
0.00001
0.000001
0.0000001
0.00000001
0.000000001
0.0000000001
0.00000000001
0.000000000001
0.0000000000001
0.00000000000001

File Name: pH.ppt

Hydroxyl Ion (OH-)

0.00000000000001
0.0000000000001
0.000000000001
0.00000000001
0.0000000001
0.000000001
0.00000001
0.0000001
0.000001
0.00001
0.0001
0.001
0.01
0.1
1

Typical pH Values
4.0% NaOH
Crackers
Blood
Pure Water
Milk
Beer
Tomatoes
Oranges
Lemons
4.9 % H2SO4

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

pH

Feb 2001

File Name: pH.ppt

8.0

9.0 10.0 11.0 12.0 13.0 14.0

pH is a Potentiometric
Measurement
pH Measuring Electrode

Feb 2001

Reference Electrode

The Measuring System

consists of a pH Measuring
Electrode and Reference
Electrode
The Potential Difference
Between the Two Electrodes
is a Function of the pH Value
of the Measured Solution
The Solution Must Be
Conductive and is Part of the
Electrical Circuit

File Name: pH.ppt

pH Sensor Components
pH Measuring Electrode

Reference Cell

KCl Buffered
to 7 pH

pH Measuring Electrode

Reference Cell

KCl Gel
Ag/AgCl Element

Feb 2001

Purpose is to Maintain a
Constant Reference Potential
Regardless of pH Change or
Other Ionic Activity in the
Solution

Reference Cell Liquid Junction

pH Sensitive Glass

Purpose is to Develop a Millivolt

Potential Directly Proportional to
the Free Hydrogen Ion
Concentration in an Aqueous
Solution

Liquid Junction

File Name: pH.ppt

Purpose is to Maintain Electrical

Contact Between the Reference
Electrode and the Measuring
Electrode by way of the Solution

How the pH Sensitive Glass

Works
Internal Fill Solution
H+

H+

H+

H+

H+

H+

Li

Internal Gel Layer

Li

pH Glass

Li

Li

External Gel Layer

Li

H+

H+

H+

Process

H+

H+

Li

Lithium Ions in the pH

sensitive glass act as current
carriers
Positive Charged Free
Hydrogen Ions (H+)Develop
Positive mV Potential
Relative to Internal Buffer
Acidic Solutions

H+

Fewer Hydrogen Ions

Relative to Internal Buffer
Produce a Negative mV
Potential
Alkaline Solutions

Feb 2001

File Name: pH.ppt

pH Temperature Slope
500

400
300
200

mV

100
0

Acids = Positive mV Signal

Base = Negative mV Signal
7.0 pH = 0 mV Output
Sensor Output Changes with
Temperature
0o C ~ 54.2 mV/pH
25oC ~ 59.2 mV/pH
50oC ~ 64.1 mV/pH

-100
-200
-300
-400

Sensor Output is Corrected

to 25oC with Automatic
Temperature Compensation

-500

pH
0C

Feb 2001

25C

50C

File Name: pH.ppt

Temperature Error in pH Units

pH Electrode Output

0.8
0.6
pH Error

0.4
0.2
0
-0.2 0

10 11 12 13 14

-0.4
-0.6
-0.8
0C

Feb 2001

10oC

20C

25C

File Name: pH.ppt

30C

40C

50C

pH Measuring Electrode

Purpose is to Develop a Millivolt Potential Directly Proportional to the Free

Hydrogen Ion Concentration in an Aqueous Solution

Process Effects
High Temperature

Faster Response / Lower Impedance

Accelerates Aging, Lithium Ions Leached from Membrane
Short Span

Low Temperature

Slower Response / Higher Impedance

Measurement > 10.0 pH

Alkaline / Sodium Ion Error

Coatings

Slower Response
Increase Zero Offset

< 50% Water

Dehydration

Steam Sterilization

Feb 2001

Dehydration
Ag/AgCl Dissolves from Silver Reference Element

File Name: pH.ppt

OHMs Law Applied to pH

E
I
10-9 Nano Amps

Feb 2001

.059 V/pH

The pH Measuring Electrode

Develops 59.2 mV per pH
Unit
pH Membrane Impedance is
Approximately 100 Meg
Ohms @ 25oC
Recommendations

R
100,000,000 Ohms

File Name: pH.ppt

Shielded Cable is Required

to Transmit a Reliable
Signal
Use Self-Powered Unity
Gain Preamplifier
Mount the Transmitter 15
feet or Less from Sensor

Temperature Affects pH
Electrode Response Time

10,000
M
e 1,000
g
o 100
h
m 10
s

pH Glass Electrode Impedance is

approximately 100 MegOhms @
25oC
For approximately every 8oC Step
Change from 25oC the pH Glass
Impedance Doubles or Halves
> 25oC Faster Response
< 25oC Slower Response

1
-5C 3C 11C 17C 25C 33C 41C 49C 57C 65C 73C

Feb 2001

File Name: pH.ppt

>1000 MegOhms pH Generally

Becomes Inoperable
Recommendations
Hold Distance Between
Transmitter and Sensor to a
Minimum
Use Low Temperature pH
Membrane

pH Electrode Life
is Temperature Dependent
Typical pH Electrode Life is
12 - 18 Months
Life is Reduced
Approximately 50% for Every
25oC Increase in Operating
Temperature
Recommendations

14
12

M
10
o
n 8
t 6
h
4
s
2
0
25C

50C

75C

100C

125C

Temperature

Feb 2001

File Name: pH.ppt

Sample Cooling
Intermittent vs Continuous
Measurement

pH Glass Electrode Options

Continuous Operation > 11.0 pH
HPH Option (High Alkaline)

Continuous Operation > 176oF (80oC)

HT Option (High Temperature)

Continuous Operation < 41oF (5oC)

LT Option (Low Temperature to -13oF (-25oC)

Hydrofluoric Acid
HF glass in 1N HCl (0.1pH)
Test Protocol (Same Electrodes)

Feb 2001

1000 ppm HF @ 20oC for 140 hrs = OK

1000 ppm HF @ 50oC for 100 hrs = OK
10,000 ppm HF @ 20oC for 100 hrs = Fail
Total time 340 hours or 14 days

File Name: pH.ppt

pH Reference Cell

Purpose is to Maintain a Constant Reference Potential Regardless of pH

Change or Other Ionic Activity in the Solution
Process Effects
Dilution of the Electrolyte
Air Entrapment
Normal Process Temperature and Pressure Fluctuations
Sugar, Organics such as Methylene Chloride, Chlorine Gas

Heavy Metal Poisoning from Lead, Mercury, Silver

Drift

Sulfide (H2S) Poisoning

Plugs Liquid Junction
Loss of Signal

High Purity Water < 100 uS/cm Conductivity

Flow Sensitivity

Low pH Values (<1.0 pH) or High pH Values (>13.0 pH)

Junction Potential Offsets

Feb 2001

File Name: pH.ppt

Reference Cell Contamination

Silver Reacts with Sulfides Forming a Non-Conductive
Precipitant at the Liquid Junction
Result is an Open Electrical Circuit Between the Measuring and
Reference
Other Undesirable Reactions that Change the Chemistry of the
Reference Half Cell are Caused by:

Feb 2001

Silver (Ag)
Lead (Pb)
Mercury (Hg)
Copper (Cu)
Bromide (Br-)
Iodide (I-)
Cyanide (Cn-)
File Name: pH.ppt

pH Control
Start, Stop, Slow Down or Speed
Up a Chemical Reaction

Feb 2001

File Name: pH.ppt

Acid Equivalents Chart

Acid Solution

.1% H2SO4
Sulfuric
1% H2SO4
Sulfuric
10% H2SO4
Sulfuric
93% H2SO4
Sulfuric
.1% HCL
Hydrochloric
1% HCL
Hydrochloric
10% HCL
Hydrochloric
37% HCL
Hydrochloric
1% HNO3
Nitric
70% HNO3
Nitric
1% H3PO4
Phosphoric
85% H3PO4
Phosphoric
1% Acetic
CH3COOH
100% Acetic
CH3COOH

Feb 2001

Weight in Kilograms (100% active) required

Volume in liters required to
to neutralize 1000 liters of acid
neutralize 1000 liters of acid
Anhydrous Caustic Soda Quick Lime Hydrated Lime Soda Ash 20% Solution 10% slurry
10% Solution
MW Norm. pH Density Ammonia
NaOH
CaO
Ca(OH)2
Na2CO3
NaOH
Ca(OH)2
Na2CO3
98

0.02

1.8

0.347

0.816

0.572

0.755

2.161

0.335

0.675

1.976

98

0.205

0.9

1.0051

3.49

8.2

5.75

7.59

21.72

3.36

6.78

19.86

98

2.17

1.0661

37

87

61

80.5

230.4

35.7

71.9

210.6

98

34.66

-1.1 1.8279

590.3

1386.9

972

1284.3

3674.1

568.6

1146.7

3358.4

36

0.027

1.6

0.467

1.097

0.769

1.016

2.906

0.45

0.907

2.657

36

0.275

0.7

1.0031

4.68

11

7.71

10.19

29.15

4.51

9.1

26.65

36

2.87

-0.4 1.0476

48.9

114.9

80.5

106.4

304.5

47.1

95

278.3

36

12.02

-1

1.185

204.7

481

337.1

445.4

1274.2

197.2

397.7

1164.7

63

0.159

0.9

1.0037

2.71

6.37

4.47

5.9

16.88

2.61

5.27

15.43

63

15.7

1.4134

267.4

628.1

440.2

581.6

1664

257.5

519.3

1521

98

0.307

1.0038

5.23

12.29

8.62

11.38

32.57

5.04

10.17

29.77

98

43.84

1.685

746.7

1754.2

1229.4

1624.3

4647.1

719.2

1450.4

4247.8

60

0.166

2.8

0.9996

2.83

6.66

4.67

6.17

17.64

2.73

5.51

16.13

60

17.45

1.2

1.0477

297.1

698.1

489.2

646.4

1849.2

286.2

577.2

1690.3

File Name: pH.ppt

Base Equivalents Chart

Base Solution

0.1% NaOH
Sodium Hydroxide
1% NaOH
Sodium Hydroxide
10% NaOH
Sodium Hydroxide
.1% NH3
Ammonia
1% NH3
Ammonia
10% NH3
Ammonia
.1% CaO
Lime
1% CaO
Lime
100 ppm Alkalinity
(as CaCO3)
1000 ppm Alkalinity
(as CaCO3)
10,000 ppm Alkalinity
(as CaCO3)

Feb 2001

Weight in Kilograms (100% active) required

Volume in liters required to
to neutralize 1000 liters of alkali
neutralize 1000 liters of alkali
Sulfuric Acid Hydrochloric Acid Carbon Dioxide Sulfur Dioxide 93% Sulfuric 37% Hydrochloric
MW Norm. pH Density
H2SO4
HCl
CO2
SO2
H2SO4
HCl
40

0.025

12

1.23

0.91

0.55

0.8

0.72

2.07

40

0.252

13

1.0095

12.37

9.2

5.55

8.07

7.28

20.9

40

2.772

14

1.1089

135.9

101.1

61

88.7

80

229.6

17

0.059

11

2.88

2.14

1.29

1.88

1.69

4.86

17

0.581

11

0.99

28.5

21.2

12.8

18.6

16.8

48.2

17

5.622

12

0.9575

275.7

205.1

123.7

179.9

162.2

465.7

56

0.036

13

1.75

1.3

1.58

1.14

1.03

2.96

56

0.361

13

1.01

17.7

13.2

15.8

11.5

10.4

29.9

100 0.001

9.4

0.049

0.0364

0.022

0.032

0.0288

0.0827

100

0.01

9.4

1.001

0.49

0.365

0.22

0.32

0.288

0.828

100 0.101

9.4

1.01

4.95

3.68

2.22

3.23

2.91

8.36

File Name: pH.ppt

pH

Titration Curve
Strong Acid with Strong Base
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9

Base Addition

Feb 2001

File Name: pH.ppt

2.1

Two Position On - Off Control

8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00

Measured variable will cycle around control point (7.0 pH)

Guidelines for control
Tank Retention Time > 5 minutes
Good Chemical Mixing, Tank turnover every two minutes
Use alarm dead band and/or delay time on/off to
compensate for minor variations in control
Feb 2001

File Name: pH.ppt

Proportional + Integral (PI) Control

8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00

Tank or Vessel retention time < 5 minutes

In-line mixing prior to sensor important
Adjust to achieve 4:1 decay ratio after process upset

Feb 2001

File Name: pH.ppt