Standard Operating Procedure RW2: Alkalinity.

Summary of Method
The method involves titrating an aliquot of the unfiltered water sample with standard
hydrochloric acid, while recording the pH. The volume of acid required to reach the end
point is calculated by plotting the Gran function, (Vo + Vt)[H+], against Vt using the pH
values recorded over about 5 mL after the Methyl Orange end point (bicarbonate to
carbonic acid end point; pH ~ 5). The end point volume, Ve, is the x intercept. This
volume of acid is used to calculate the alkalinity of the sample in milliequivalents per
litre.
Quality Control Data
Sampling duplicates should be taken at sufficient sampling sites so as to generate at least
3 sampling duplicates.
With three titration groups split the samples between them and then each group should do
their samples and then as many of the other pair’s samples as time allows.
The standardization of the acid should be done in duplicate by each group.
Glass and plastic ware:
All glass and plastic ware should be rinsed once with 10% HCl and then three times with
small aliquots of deionized water before use. After the analyses glassware should be
rinsed twice with deionized water before being stored. Always store volumetric flasks
with their stoppers in place.

Experimental Procedure
Standardization of the 0.04 mol dm-3 HCl solution
Fill the burette with the supplied 0.04 mol dm-3 HCl and record the burette reading.
Pipette 5 ml of the standard sodium carbonate solution into a 250 ml beaker, dilute to
about 100 mL with distilled water, add 3 or more drops of methyl orange (MO) indicator
to give a faint orange colour, place the calibrated pH electrode into the solution, stir
thoroughly and record the pH once it has stabilized. Leave the electrode in the solution
until the titration is complete.
After recording the initial burette and pH readings, start the titration by adding about 1 ml
of the approximately 0.04 mol dm-3 HCl acid from the burette, stirring the solution and
recording the burette reading and pH after the pH has stabilized. Continue adding 1 mL at
a time while recording the burette readings and pHs until the pH is 5. The colour of the
solution should be starting to change from orange to pink. Be careful to stir the solutions
thoroughly after each addition of acid and only record the pH after it has stabilized.
Continue the titration as above but adding the acid in 0.5 mL aliquots, mixing thoroughly
and recording the burette readings and pHs once the pH is steady after each addition of
acid. Continue this process until 4 mL have been added after the pH is less than 5 (the
colour should have changed at about pH 5). Do the standardization in duplicate, you
should not need to use more than 10 mL of acid per standardization.

Determination of Alkalinity
Using a measuring cylinder transfer 100 ml of the water sample to a 250 ml beaker and
add 3 drops of methyl orange indicator. Place the calibrated pH electrode into the
solution and record the pH and the initial burette reading. Do not remove the electrode
from the solution until the titration is complete.
Titrate the samples with the approximately 0.04 mol dm-3 HCl in the same way as you did
for the acid standardization (1 ml at a time to pH 5 and then 0.5 mL at a time until 4 mL
have been added after the pH < 5).

You should not need more than about 8-10 mL acid per titration.
Equipment
One pH meter and electrode.
Three glass stirring rods.
One 25 ml burette.
One 5 ml pipette and pipette filler.
One 100 ml measuring cylinder
Three 250 ml beakers.
One 250 ml volumetric flask.
One 600 mL beaker.
One titration stand, clamp and tile.
Chemicals
Distilled water.
Methyl orange indicator.
Sodium Carbonate, AR.
Hydrochloric Acid, concentrated.
Buffer solutions (pH 4, 7 and 10).
10% HCl cleaning acid
Dilute 250 ml conc. HCl to 2.5 L in a clean 2.5 L glass bottle.

Preparation of Standard Sodium Carbonate Solution, 0.05 mol dm-3

Dissolve 1.3 g, accurately weighed (record the weight), AR sodium carbonate (pre-dried
at 250 C) and dissolve it in deionized water and make up to the mark in a 250 ml
volumetric flask. Store in a well cleaned plastic bottle. The solution can only be stored
for two days.
Preparation of Hydrochloric Acid, 0.04 mol dm-3

Dilute 2 ml (measuring cylinder) of concentrated HCl to 500 ml (beaker) with deionized

water. Mix thoroughly. Store in a clean plastic bottle.
Calculations
1. Concentration of Na2CO3:
Moles Na2CO3 dissolved in 100 mL = wt/RMM = wt/(23*2+12+48) moles.
∴ [Na2CO3] = wt/(106)/100*1000 mol dm-3
2. Calculation of equivalence volumes for HCl standardization and water alkalinity:
a) For each titration reading AFTER the colour change calculate [H+] = 10-pH.
b) For each titration reading after the colour change calculate (Vo + Vt) where Vo is
the sample (or volume of diluted Na2CO3: 100 mL in both cases) and Vt is the titre
volume.
c) For each titration reading after the colour change calculate (Vo + Vt)* [H+].
d) Plot (Vo + Vt)* [H+] (y axis) against Vt (x axis) and draw a straight line through
the points that form a straight line. Where that line crosses the x-axis gives the
equivalence volume Ve1 or Ve2 (see below).
3. Concentration of HCl:

Titration reaction: CO32- + 2H+ ⇋ H2CO3.

∴ 2 moles of protons for each mole of CO32-.

Moles CO32- in 5 mL = {[Na2CO3]/1000*5} moles.

If the volume of HCl used = Ve1.
Moles H+ in Ve1 = 2*{[Na2CO3]/1000*5} moles

∴ [HCl] = 2*{[Na2CO3]/1000*5}/Ve1*1000 mol dm-3.

4. Alkalinity of sample:

Titration reaction: B- + H+ ⇋ HB where B is any mono-protic base present in the sample.

∴ 1 mole of protons for each mole of B -.

If volume of acid required to titrate the water sample = Ve2.

∴Moles H+ in Ve2 = {[HCl]/1000*Ve2} moles

∴ moles mono-protic base in 100 mL of water sample = {[HCl]/1000*Ve2} moles

∴ concentration of base in water sample = {[HCl]/1000*Ve2}/100*1000 mol dm-3.

or {[HCl]/1000*Ve2}/100*1000*1000 millimol dm-3

However since we do not know which bases are present we assume they are all
mono-protic and so use units of milliequivalents dm-3.

(Revised 17th October, 2016, AMG)