Title : Concept of pH

Date: 19/03/2020
Name of Faculty: Mr. Darshan Salunke
Lecture No : 5 (as per TT)

SHROFF S R ROTARY INSTITUTE OF CHEMICAL TECHNOLOGY 1

 pH
Intensity factor of acidity and indicates
– hydrogen ion activity
– intensity of acidic or basic character of a solution at a given temperature
– N/10 solution of H2SO4 and of acitic acid do not show same pH (depends on dissociation
and H+ ion release)
Most important and most frequently measured parameter Neutralization,
softening, coagulation, precipitation,
disinfection, corrosion control, etc., aspects of water
supply and wastewater treatment are pH dependent
Buffer capacity: Amount of strong acid or base needed to change pH of 1 liter of
sample by one pH unit
 pH
Ion product of water H OH  K  1.0110
 
w
14
at 25 C
At neutral pH
H  OH 1.00510
  7

pH is defined as pH   log H   
pH  pOH  pK w  14
pKw is constant for a given temperature
Neutral pH varies with temp. (7.5 at 0C & 6.5 at 60C) If pH increases pOH
decreases and vice-versa
Natural water pH is in the range of 4-9
Natural waters are slightly basic due carbonates and bicarbonates
Relationships exist between pH, acidity and alkalinity
 pH measurement: pH meter
pH meter is used
– Involves potentiometric measurement of hydrogen ion activity
– capable of reading both pH and millivolts
– A pH meter with good electrodes measures pH with 0.1 pH units accuracy under normal
conditions
pH meter has
– A potentiometer
– A glass electrode
– A reference electrode
– A temperature compensation device
pH meters usually have two controls
– Intercept control – parallelly shifts the response curve, between emf and pH, for giving 0
emf with pH 7 buffer
– Slope control – rotates response curve about isopotential point
 pH measurement: pH meter
Glass electrode
– A sensor electrode
– Electro motive force (emf) produced in the glass electrode
system linearly varies with the pH of the sample
– Using buffers of known pH values emf is measured by glass electrode system and plotted
against pH for calibrating the meter
– With the calibrated meter emf produced by the sample is measured and pH is estimated by
extrapolation and interpolation
Reference electrode
– A half cell providing constant electrode potential
– Calomel electrode or silver: silver chloride electrode is used
– Has a liquid junction
– The electrode is filled by an electrolyte to proper level to ensure proper wetting of the liquid
junction
Combination electrode: both glass electrode and reference electrode are
incorporated into a single probe
 Electrode storage
Keep the electrodes wet when the pH meter is not in use
– Follow manufacturer’s instructions
– Use tap water with conductivity >4000 µmhos/cm rather than
distilled water for short-term electrode storage
– pH 4 buffer is best for glass electrode storage
– Saturated KCl solution is good for glass electrodes and combination electrodes
Before use remove electrodes from storage solution, rinse
with distilled water, and blot dry with soft tissue
– Rinsing and blotting dry are also needed for electrode transfer from one solution to the
next
Prior to use, conditioning of the electrode in a small portion
of the sample for a minute is recommended
– in case of poorly buffered samples the conditioning can be in 3 or 4 successive portions of
the sample
– The conditioned electrode is not rinsed, it is only blot dried
 Calibration of pH meter
Transfer electrode(s) into a standard buffer of neutral pH and set isopotential
point on the meter (point of ‘0’ emf)
Transfer electrode(s) into 2nd standard buffer of pH within 2 units from the sample
– Ensure same temperature for both sample and 2nd buffer
– Record temp. and adjust temp. on the meter
– Adjust meter pH to that of the buffer
Transfer electrode(s) to 3rd standard buffer of pH <10 and within 3 pH units from
the sample
– Check if the meter pH is within 0.1 units of the actual - If not then the pH meter is faulty
Calibration frequency
– needed prior to each set of pH measurements
– If pH values vary widely within a set, check with a 3rd buffer of pH within 1 or 2 units from the
sample is needed
 pH measurement: Buffer solutions

Standard buffer solutions of known pH are needed for pH meter calibration

– Commercially available buffer tablets, powders or solutions can
be used
– can be prepared in the laboratory in distilled water
– 10.12 g of potassium hydrogen phthalate in 1000 ml solution made in distilled water
gives 4.004 pH at 25C
– 2.092 g of NaHCO3 and 2.64 g of NaCO3 in 1000 ml solution
made in distilled water gives 10.014 pH at 25C
– Distilled water with <2µmhos/cm conductivity is used after boiling and cooling (pH should
be 6-7 after addition of a drop of saturated KCl solution per 50 ml)
pH of buffer solutions change with temperature
– One can refer standard tables for pH of various buffer solutions at different temperatures
 pH meter: Trouble shooting

To know whether the problem is with the meter

– Disconnect electrodes using short-circuit strap
– Connect reference electrode terminal to glass electrode terminal
– Observe pH change with calibration knob adjustment - rapid and even
response over wide range indicates no problem with the meter
– Switch to milliVolt scale – if the meter reads zero then there is no problem
with the meter
To know whether the problem is with the electrode pair
– Substitute one electrode at a time and cross check with two buffers (4 pH
units apart) – deviation <0.1 pH units indicates no problem with the
electrode
 pH meter: Trouble shooting
Failure of glass electrode
• Scratches, deterioration or accumulation of debris can be responsible
• Rejuvenate the electrode by alternatively immersing 3 times in 0.1 N NaOH
and 0.1 N HCl
• If not rejuvenated then do
– immerse the electrode in KF solution for 30 seconds
– soak in PH 7 buffer overnight
– rinse and store in 7 pH buffer
– rinse in distilled water prior to use
• KF solution: 2 g of KF in 2 ml conc. H2SO4, dilute
resultant solution to 100 ml with distilled water
If protein coat is suspected on glass electrode remove it by soaking in 10%
pepsin solution adjusted to 1-2 pH
 Precautions relating to pH measurement

Use of special low sodium error electrodes is needed for measuring pH >10, at
high temperature, accurately
Liquid membrane electrodes are good for pH below 1
pH measurement can not be made accurately in non- aqueous media,
suspensions, colloids or high ionic strength solutions
Temperature can affect pH measurement by
– Changing the properties of the electrodes
– Brining in chemical equilibrium changes
Buffer solutions deteriorate from mold growth or contamination hence replace
them every 4 weeks once
Store buffer solutions and samples in polyethylene bottles
1. Explain the concept of pH
2. Explain the construction of pH meter.

SHROFF S R ROTARY INSTITUTE OF CHEMICAL TECHNOLOGY 12