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  Base dissolves in

+
water to furnish H water to furnish OH-
ions ions
• HCl H+ + • NaOH +
Na +
Cl- OH
-

• HNO3 H+ + • KOH K+ -
+ OH
NO3-
+ -
• NH4OH NH4+ +
• HF H + F -
OH

Feb 2001 File Name: pH.ppt

 Ion Concentration (mol/l)
pH Hydrogen Ion (H+) Hydroxyl Ion (OH-)
Acid 0 1 0.00000000000001
1 0.1 0.0000000000001
2 0.01 0.000000000001
3 0.001 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
11 0.00000000001 0.001
12 0.000000000001 0.01
13 0.0000000000001 0.1
Alkaline 14 0.00000000000001 1

Feb 2001 File Name: pH.ppt

 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 8.0 9.0 10.0 11.0 12.0 13.0 14.0

pH

Feb 2001 File Name: pH.ppt

 pH is a Potentiometric
Measurement

pH Measuring Electrode 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

Feb 2001 File Name: pH.ppt

 pH Sensor Components
 pH Measuring Electrode
pH Measuring Electrode Reference Cell
• Purpose is to Develop a Millivolt
Potential Directly Proportional to
the Free Hydrogen Ion
Concentration in an Aqueous
Solution
KCl Buffered  Reference Cell
to 7 pH • Purpose is to Maintain a
Constant Reference Potential
KCl Gel
Regardless of pH Change or
Ag/AgCl Element
Other Ionic Activity in the
Solution
 Reference Cell Liquid Junction
• Purpose is to Maintain Electrical
Contact Between the Reference
Electrode and the Measuring
pH Sensitive Glass Liquid Junction Electrode by way of the Solution

Feb 2001 File Name: pH.ppt

 How the pH Sensitive Glass
Works
 Lithium Ions in the pH
sensitive glass act as current
Internal Fill Solution carriers
 Positive Charged Free
H+ H+ H+ H+ H+ H+ H+
Hydrogen Ions (H+)Develop
Li Internal Gel Layer Li Positive mV Potential
Relative to Internal Buffer
Li
pH Glass Li
• Acidic Solutions
Li External Gel Layer Li
 Fewer Hydrogen Ions
H+ H+ H+ H+ H+
Relative to Internal Buffer
Produce a Negative mV
Process Potential
• Alkaline Solutions

Feb 2001 File Name: pH.ppt

 pH Temperature Slope
500
 Acids = Positive mV Signal
400

300
 Base = Negative mV Signal
200  7.0 pH = 0 mV Output
100  Sensor Output Changes with
Temperature
mV

0
-100 • 0o C ~ 54.2 mV/pH
0

10

12

14
-200 • 25oC ~ 59.2 mV/pH
-300 • 50oC ~ 64.1 mV/pH
-400
 Sensor Output is Corrected
-500
to 25oC with Automatic
pH
Temperature Compensation
0C 25C 50C

Feb 2001 File Name: pH.ppt

 Temperature Error in pH Units
pH Electrode Output
0.8
0.6
0.4
0.2
pH Error

0
-0.2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

-0.4
-0.6
-0.8
0C 10oC 20C 25C 30C 40C 50C

Feb 2001 File Name: pH.ppt

 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
• Dehydration
• Ag/AgCl Dissolves from Silver Reference Element

Feb 2001 File Name: pH.ppt

 OHM’s Law Applied to pH
 The pH Measuring Electrode
Develops 59.2 mV per pH
Unit
E .059 V/pH  pH Membrane Impedance is
Approximately 100 Meg
Ohms @ 25oC
 Recommendations
• Shielded Cable is Required
I R to Transmit a Reliable
Signal
• Use Self-Powered Unity
Gain Preamplifier
10-9 Nano Amps 100,000,000 Ohms • Mount the Transmitter 15
feet or Less from Sensor

Feb 2001 File Name: pH.ppt

 Temperature Affects pH
Electrode Response Time
 pH Glass Electrode Impedance is
10,000 approximately 100 MegOhms @
25oC
M
 For approximately every 8oC Step
e 1,000 Change from 25oC the pH Glass
g Impedance Doubles or Halves
o 100  > 25oC Faster Response
h  < 25oC Slower Response
m 10 • >1000 MegOhms pH Generally
s Becomes Inoperable
• Recommendations
1 • Hold Distance Between
Transmitter and Sensor to a
-5C 3C 11C 17C 25C 33C 41C 49C 57C 65C 73C Minimum
• Use Low Temperature pH
Membrane

Feb 2001 File Name: pH.ppt

 pH Electrode Life
is Temperature Dependent
 Typical pH Electrode Life is
14
12 - 18 Months
12
M  Life is Reduced
10 Approximately 50% for Every
o
n 8 25oC Increase in Operating
t 6 Temperature
h  Recommendations
4
s • Sample Cooling
2
• Intermittent vs Continuous
0
Measurement
25C 50C 75C 100C 125C
Temperature

Feb 2001 File Name: pH.ppt

 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)
• 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

Feb 2001 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:
• Silver (Ag)
• Lead (Pb)
• Mercury (Hg)
• Copper (Cu)
• Bromide (Br-)
• Iodide (I-)
• Cyanide (Cn-)

Feb 2001 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
Weight in Kilograms (100% active) required Volume in liters required to
Acid Solution 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

.1% H2SO4 98 0.02 1.8 1 0.347 0.816 0.572 0.755 2.161 0.335 0.675 1.976
Sulfuric
1% H2SO4 98 0.205 0.9 1.0051 3.49 8.2 5.75 7.59 21.72 3.36 6.78 19.86
Sulfuric
10% H2SO4 98 2.17 0 1.0661 37 87 61 80.5 230.4 35.7 71.9 210.6
Sulfuric
93% H2SO4 98 34.66 -1.1 1.8279 590.3 1386.9 972 1284.3 3674.1 568.6 1146.7 3358.4
Sulfuric
.1% HCL 36 0.027 1.6 1 0.467 1.097 0.769 1.016 2.906 0.45 0.907 2.657
Hydrochloric
1% HCL 36 0.275 0.7 1.0031 4.68 11 7.71 10.19 29.15 4.51 9.1 26.65
Hydrochloric
10% HCL 36 2.87 -0.4 1.0476 48.9 114.9 80.5 106.4 304.5 47.1 95 278.3
Hydrochloric
37% HCL 36 12.02 -1 1.185 204.7 481 337.1 445.4 1274.2 197.2 397.7 1164.7
Hydrochloric
1% HNO3 63 0.159 0.9 1.0037 2.71 6.37 4.47 5.9 16.88 2.61 5.27 15.43
Nitric
70% HNO3 63 15.7 1.4134 267.4 628.1 440.2 581.6 1664 257.5 519.3 1521
Nitric
1% H3PO4 98 0.307 1 1.0038 5.23 12.29 8.62 11.38 32.57 5.04 10.17 29.77
Phosphoric
85% H3PO4 98 43.84 1.685 746.7 1754.2 1229.4 1624.3 4647.1 719.2 1450.4 4247.8
Phosphoric
1% Acetic 60 0.166 2.8 0.9996 2.83 6.66 4.67 6.17 17.64 2.73 5.51 16.13
CH3COOH
100% Acetic 60 17.45 1.2 1.0477 297.1 698.1 489.2 646.4 1849.2 286.2 577.2 1690.3
CH3COOH

Feb 2001 File Name: pH.ppt

 Base Equivalents Chart

Weight in Kilograms (100% active) required Volume in liters required to

Base Solution 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

0.1% NaOH 40 0.025 12 1 1.23 0.91 0.55 0.8 0.72 2.07

Sodium Hydroxide
1% NaOH 40 0.252 13 1.0095 12.37 9.2 5.55 8.07 7.28 20.9
Sodium Hydroxide
10% NaOH 40 2.772 14 1.1089 135.9 101.1 61 88.7 80 229.6
Sodium Hydroxide
.1% NH3 17 0.059 11 1 2.88 2.14 1.29 1.88 1.69 4.86
Ammonia
1% NH3 17 0.581 11 0.99 28.5 21.2 12.8 18.6 16.8 48.2
Ammonia
10% NH3 17 5.622 12 0.9575 275.7 205.1 123.7 179.9 162.2 465.7
Ammonia
.1% CaO 56 0.036 13 1 1.75 1.3 1.58 1.14 1.03 2.96
Lime
1% CaO 56 0.361 13 1.01 17.7 13.2 15.8 11.5 10.4 29.9
Lime
100 ppm Alkalinity 100 0.001 9.4 1 0.049 0.0364 0.022 0.032 0.0288 0.0827
(as CaCO3)
1000 ppm Alkalinity 100 0.01 9.4 1.001 0.49 0.365 0.22 0.32 0.288 0.828
(as CaCO3)
10,000 ppm Alkalinity 100 0.101 9.4 1.01 4.95 3.68 2.22 3.23 2.91 8.36
(as CaCO3)

Feb 2001 File Name: pH.ppt

 Titration Curve
Strong Acid with Strong Base

14
13
12
11
10
9
8
pH

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 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1

Base Addition

Feb 2001 File Name: pH.ppt

 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