How to measure the pHPZC using the pH drift method

Km Ganesh - Sri Sathya Sai Institute of Higher Learning

Anantapur, Andhra Pradesh, India
2015
• Make 0.01 M solution of NaCl.

• Take 50 ml of this solution and bubble it with Nitrogen gas to expel the dissolved CO2
for few minutes in a jacketed titration vessel at room temperature (25 degree Celsius) till
you get a stable pH reading. If nitrogen gas bubbling is not feasible in your lab then some
researchers boil the water to get rid of dissolved CO2 and they keep it in an air tight
condition. Basically, the initial pH should be stable, which varies under exposure to open
air because of dissolution of CO2 which leads to reduction of pH.

• Then adjust the pH of the NaCl solution to pH 2 (use HCl or NaOH solutions for pH
adjustment) [Add few drops at a time and see the trend of change in pH. See that you
don’t end up adding too much HCl or NaOH solution fluctuating up and down around 2
in the effort of getting exact pH 2! Even if it is 1.8 to 1.9 or 2.1 or 2.2, stop there. Note
the initial pH reading once it is stabilized under a close jacketed air tight condition. Add
150 mg of material into the flask containing 50 ml of NaCl solution already adjusted to
pH 2 and keep it for shaking for 24 h in an air tight condition at 200 rpm and 25 degree
Celsius.

• Repeat the same process to get Initial pH of 4, 6, 8, 10 and 12, and then add 150 mg of
adsorbent material after the pH adjustment, and keep each of them for shaking at 200
rpm for 24 hrs.
Note: a. Add the material into the solution after the initial pH is adjusted to 2,4,6,8,10,12.
b. You can scale down the material by half, say 75 mg/25 ml in case you are short
of material and, also take the reading for pH range of 2 to 10 instead of pH range of
2 to 12.
• After 24 h of shaking, filter and measure the final pH for each set.
• Plot the final pH (y axis) vs Initial pH (x axis) as shown in figure 1.

Figure 1. pH final vs pH initial.

• Draw a line where initial pH is equal to final pH as shown by the black line in the figure
1.

• As you can see in the figure 1, initial pH 12 led to final pH 11.2, implying that the
adsorbent material is of positive surface charge or acidic [Which attracts and adsorbs
the hydroxide ions from the solution (from the hydronium-hydroxide equilibrium in any
aqueous solution) and reduces its pH from 12 to 11.2]

• Same happens to the set with initial pH 10 that comes down to around pH 8. Next, we
check the final pH for 6. It is clearly on the region (above the middle diagonal line) where
the final pH is above 7 where the initial pH was 6. Implying? The adsorbent surface has
become negative in charge (Basic character) and is removing the positively charged
hydronium ions from the aqueous media. Thus, the final pH is more than initial pH as
reflected in the graph.
Remember: More pH implies less H3O+ ions in the system and lesser the pH implies more
H3O+ ions in the solution. Just to be specific here: solution with pH 2 has 10 times more
hydronium ions in the solution compared to pH 3 or 100 times more than pH 4 or 1000 time
more than pH 5 and so on. It is logarithmic scale, isn’t it?
• Now we have to find the point of transition of the adsorbent material where the surface
charge becomes negative (green zone in the diagram) from the positive (red zone), i.e.
the point where it turns basic from acidic (at the transition the charge will be zero). We
connect the point for pH 8 and pH 6 and see that the line cuts the black diagonal line at
pH 7.4 in this particular case. At this pH the surface charge of the material is zero. Here
is the point where both the initial and the final pH is same after the 24 h shaking.