CHEMISTRY 12

Module 2: The Acidic

Environment

9.2 Volumetric Analysis

9.2 Volumetric Analysis

volumetric analysis = a form of chemical

analysis in which the concentration or
amount of a substance A (the unknown) is
determined by measuring the volume of
solution of accurately known
concentration of another substance B
(the standard) which is just sufficient to
react with all of the sample A.

The process of determining the "just

sufficient" volume is called titration.

The equivalence point of a chemical rxn

is the point at which the amounts of the
2 reactants are just sufficient to cause
complete consumption of the 2
reactants

reactants are in stoicheometric

(proper mole:mole) ratio with each
other, no excess of acid or base present

The end point is the point where the

indicator has just changed colour
indicating a slight excess of one of the
reactants

The endpoint is reached fractionally

after the equivalence point.
Acid Base Titrations (basic steps)

1. wash a burette with distilled water and then

rinse with a little of the solution to be placed in
it (3 times)

2. fill burette with a solution of known

concentration (soln A) and adjust level to the
zero mark

3. wash a pipette with water and then rinse with a

little of the solution (soln B) to be placed in it
(3 times)

4. wash a conical flask with distilled water

5. use a pipette to transfer an exact volume, and

hence exact number of moles of the solution
(soln B) into the conical flask
6. add on or two drops of indicator to the conical flask

7. slowly run soln A from the burette into the conical

flask with continuous swirling and washing of the
inside of the conical flask until the indicator just
changes colour

8. accurately record the volume delivered from the

burette into the flask

9. calculate the concentration of sol'n B using C=n/V and

mole:mole ratios
Primary Standards and Standard Solutions

- cannot make solutions of exact concentrations of common

acids and bases because some absorb water and react with
carbon dioxide in air to form carbonates.

a primary standard
must be obtainable in pure form, free of moisture
must be stable, cannot absorb water or other substances from
atmosphere during weighing or when in use
must be a crystalline solid and hence able to be accurately weighed
out
must have a relatively high molecular mass to minimise weighing
errors
must be readily soluble in distilled water and react to completion
must react instantaneously and to completion

resulting solution called standard solution

 Na2CO3 and NaHCO3 make suitable primary standards since after
drying have high purity, can be accurately weighed, and
dissolve in water.

NaOH and HCl are not suitable primary standards. NaOH

absorbs water and CO2 from the air. HCl obtained
commercially is only approximately 10 molar.

When diluting acids, always add water to acid and not vice
versa (awwww not waaaa!!!) the dilution of acids is extremely
exothermic. It is safer for the heat to be dissipated through
the water than through concentrated acid.
 Preparing a Standard Solution

1. primary standard must be pure and dry
2. weigh as accurately as possible
3. thoroughly clean volumetric flask (rinse
with distilled water (3 times)
4. transfer all solid to flask
5. solute must be completely dissolved
6. volume of solution must be accurate
(bottom of meniscus up to mark in
volumetric flask)
7. pure water (distilled or deionized) must
be used for solns and rinsing
8. shake volumetric flask well to ensure
uniform mixing before filling burettes.
Glassware

- must be cleaned and rinsed several times (with distilled water)

- pipettes and burettes must be rinsed with a portion of the soln

pipettes rinse with soln first

- overfill, then let slowly out til bottom of meniscus is at line
- hold at eye level for reading
- let soln drain out never blow!
- hold pipette tip on side of flask at 45 degree angle til drained (20sec)
- leave remaining liquid in (its meant to be there!)
burettes rinse with soln first (3 times)
overfill, let xs run out until meniscus is
on exact zero (make sure no air
bubbles!)
clamp vertically
hold white card behind burette to read
read to nearest 0.01mL
near end point, let out very slowly
let a drop build up on tip and rinse with
distilled water

pipettes & burettes accuracy = +/-0.5%

(measuring cylinders = +/- 5%)

Choice of Indicators

need sharp colour change at the appropriate pH

can also use a pH meter

When you titrate a STRONG base with a STRONG acid, the
equivalence point will be 7.

Bromothymol blue would be a good indicator as it changes colour

around pH 7.

ex) hydrochloric acid + sodium hydroxide

When you titrate a WEAK base with a STRONG acid, the equivalence point
will less than 7.

Methyl orange would be a good indicator as it changes colour around pH 3-4.

ex) hydrochloric acid + ammonium hydroxide

When you titrate a STRONG base with a WEAK acid, the equivalence
point will greater than 7.

Phenolphthalein would be a good indicator as it changes colour

around pH 9.

ex) acetic acid + sodium hydroxide

Titration with an indicator is not used for WEAK acid with a WEAK
base as there is no sudden change in pH to indicate the equivalence
point.

ex) acetic acid + ammonia

Titration Equiv Pt Indicator
Strong Acid 7 Bromothymol
Strong Base blue pH 6.2 7.6
Strong Acid <7 Methyl orange pH
Weak Base 3.1 4.4
Weak Acid >7 Phenolphthalein
Strong Base pH 8.3-10
Titration Calculations

Example 1
A std soln of sodium hydrogen carbonate has a concentration of 0.100mol/L.
A 25.00mL aliquot of the std base was titrated against an unknown sulfuric acid
soln using methyl orange indicator. The avg titre at the end point was 28.35mL.
Calc the conc of the sulfuric acid soln.

1) Write a balanced equn: H2SO4(aq) + 2NaHCO3(aq) Na2SO4(aq) + 2H2O(l) + CO2(g)

2) Write what you know:
cNaHCO3 = 0.100mol/L
VNaHCO3 = 25mL = 0.025L
VH2SO4 = 28.35mL = 0.02835L
cH2SO4 = ?
3) Find moles NaHCO3: n = c x V = (o.100mol/L) x(0.025L) = 0.0025mol
4) Find moles H2SO4 (mol:mol ratio): n = (0.0025mol) = 0.00125 mol
5) Find conc H2SO4: c = n /V = 0.00125mol /0.02835L = 0.0441 mol/L
Example 2
15.922g Na2CO3 dissolved in water and made up to 500mL in a volumetric flask.
25mL of this soln was then titrated with 0.4 mol/L soln of HCl. It required
38.2mL of acid to reach the endpoint. Determine the molarity of HCl soln.

1) Write a balanced equation:

Na2CO3(aq) + 2HCl(aq) 2NaCl(aq) + CO2(g) + H2O(l)
2) Write what you know:
mNa2CO3 = 15.922g VorigNa2CO3 = 500mL = 0.500L Vfinal = 25mL = 0.025L
cHCl = 0.4mol/L VHCl = 38.2mL = 0.0382L
3) Calculate [Na2CO3] soln:
n = m/M = 15.922g / 106.0 = 0.1502 mol
c = n/V = 0.1502 / 0.500L = 0.3004 mol/L
3) Calc moles of Na2CO3 used (in 25 mL):
n = c x V = (0.3004mol/L)x(0.025L) = 0.0075mol
4) Calc moles of HCl (mol:mol ratio)
n = (2/1)(0.0075) = 0.150mol
5) Calc [HCl] (use 38.2 mL)
c = n/V = 0.0150mol/0.0382L = 0.393mol/L
Example 3
Vinegar is usually 4-5% acetic acid. To find [CH3COOH] of a specific
brand, a chemist diluted 10mL of vinegar to 100mL, then took 25 mL
of diluted soln and titrated with 0.105 mol/L NaOH. 15.9mL of
NaOH was needed to neutralise vinegar. Calc molarity & % (w/v) of
orig vinegar.

CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(l)

nNaOH = c x V = (0.105mol/L)(0.0159L) = 1.67 x 10-3 mol

nCH3COOH = nNaOH = 1.67 x 10-3 mol (1:1 ratio)
[CH3COOH] dilute: c = n/V = 1.67 x 10-3 mol / 0.025L = 0.668 mol/L
[CH3COOH] orig: c1V1 = c2V2 c1 x (0.010L) = (0.0668mol/L) x (0.100L)
c1 = 0.668mol/L
%(w/v) per 100mL: 0.668mol/100mL
m = nxM = (0.0668mol)(60g/mol) = 4.01g
4.01g/100mL = 4.01%(w/v)
Neutralisation and Safety

Many acids and bases are corrosive so we must neutralise spills

Dont use conc acids or bases to neutralise as danger if too much used +
exo rxn
NaHCO3 (sodium bicarb) amphiprotic so can be used for both acid and
base spills

Adv: - stable so easily stored and transported

- amphiprotic (HCO3- + H+ H2O + CO2 ; HCO3- + OH- CO32- + H2O)
- cheap so can be used on industrial scale
- xs not dangerous as not too strong
Worksheet 12
9.2 questions
9.2 prac std solns
9.3 pH of vinegar