CHAPTER 2

Acid-Base Titrations
IN THESE titrations, a solution of an acid is added to a solution of
a base, until the base is exactly neutralized and neither acid nor
base is in excess. Similarly a base may be added to an acid until
the neutralization is exactly complete. The quantities of acid and
base are then exactly equivalent, and if the concentration of one
solution is known that of the other solution may be calculated.
For example, a solution of sodium hydroxide may be titrated
with hydrochloric acid :

N a + + O H " + H 3 0 + + C I " -> N a + + C I " + 2 H 2 0

(H3O+ Ξ H + H 2 0 ) t
Hence N a O H = HCl = 1 equivalent.
Thus the equivalent weight of hydrochloric acid
= the molecular weight of sodium hydroxide

and the equivalent weight of sodium hydroxide

= the molecular weight of sodium hydroxide
If, for example,
25-65 ml 0-110 Ν hydrochloric acid
= 25*00 ml χ Ν sodium hydroxide
/25*65 χ 0-110\ = χ
X
\ 25*00 )
0-1129 = x.
t There is experimental evidence for the proton being attached to a group
of four water molecules, the latter being linked by hydrogen bonding.
24
 ACID-BASE TITRATIONS 25

Normal sodium hydroxide contains 1 gram mole, that is 40-00 g

per litre solution.
0-1129 Ν sodium hydroxide contains (40-00 χ 0-1129) g per
litre of solution
= 4-516 g per litre.
Concentration of the sodium hydroxide solution is 4-52 g per litre.

Similarly:
2KOH + H 2 S 0 4 = K 2 S 0 4 + 2 H 20 .
Hence K O H = i H 2 S 0 4 = 1 equivalent,
and Ba(OH)2 + 2 H N 0 3 = B a ( N 0 3) 2 + 2 H 20 .
Hence i B a ( O H ) 2 = H N 0 3 = 1 equivalent.

The equivalence point is shown by means of an indicator having

one colour in acid solution and another colour in alkaline
solution. At the neutralization point it shows an intermediate hue.

Choice of indicator for a particular titration

Strong acids, when pure, are substances whose bonding is
largely covalent in character. They react with water to give
+
hydroxonium ions (a hydrated proton H - H 2 0 or H 3 0 + ) and
anions :
HX + H 2 0 - > H 3 0 + + X ~
where X " represents an anion. Examples of such acids are hydro-
chloric, sulphuric and nitric acids.
Weak acids react in this way to a limited extent only, t h u s :

HX + H2O^H30++X~

and so their solutions are low in hydroxonium ion concentration.

Examples of these acids are phosphoric, boric, acetic, oxalic and
carbonic acids.
Strong bases are ionic compounds which contain the hydroxyl
ion, O H -. Examples of such bases are sodium, potassium and
26 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

barium hydroxides. Weak bases react slightly with water to give

some hydroxyl ions, thus ammonia reacts with water:

N H 3 + H 2 0 ^ . ( N H 4) + + ( Ο Η Γ

and the anions of sodium carbonate a n d borax react with water:

( C 0 3) 2 ~ + H 2 0 ^ ( H C 0 3) - + (OH)-
and (HCO3)" + H 20 ^ H 2C 0 3 + (OH)"

( B 40 7) 2 - + H 2 0 ^ ( H B 4 0 7 ) - +(OH)"

and (HB4O7)- + H 2 0 ^ H 2B 40 7 + (OH)".

If a salt derived from a strong acid and a strong base is dissolved
in water, the solution has the same hydrogen ion concentration as
that of pure water (i.e. p H 7). When neutralization occurs in
strong acid/strong base titrations, there is a large change in p H
for a small volume of added titrant and almost anyindicator will
show when the end-point is reached. However, in the case of a
salt formed from a weak acid a n d a strong base, the aqueous
solution is on the alkaline side of absolute neutrality and so when
equivalent amounts of acid and base are present, the solution will
have a hydrogen ion concentration smaller than that of pure
water (i.e. p H will be greater than p H 7). Also, the change in
hydrogen ion concentration for added titrant is much smaller.
Thus to ensure that the end-point and the equivalence point
practically coincide, only an indicator which changes colour over
the appropriate p H range may be used. The indicator Phenol-
phthalein has a p H range of 8-4-10Ό and is thus suitable for
titrations of many weak acids with strong bases. Methyl orange
(pH range 2-8-4-6) and methyl red (pH range 4-4-6-0) are used
in cases of weak bases with strong acids. Screened methyl orange
indicator contains the indicator and a blue dyestuff, giving an
additive colour effect. Methyl orange appears red in acid
solution and orange-yellow in alkaline solution but the
intermediate orange-red colour is difficult to detect precisely. I n
screened methyl orange the colour is magenta in an acid solution,
green in an alkaline solution and grey in neutral solution. Since
 Table of some indicators
Indicator's
Titration Examples Some suitable colour change, pH range Indicator solution
type indicators acid-alkaline concentration

Strong acid HCl, H 2 S 0 4 , H N 0 3 , Any indicator,

and NaOH, KOH, Phenolphthalein
strong base Ba(OH) 2 often preferred

Strong acid (as above) Methyl orange Red to 2-8-4-6 0-05 g indicator in 100 ml

ACID-BASE TITRATIONS
and orange-yellow water
weak base N a 2C 0 3, N a 2 B 4 0 7
KHCO3, NH4OH
Screened Magenta to 3-0-4-6 0 1 g indicator and 0-14 g
methyl orange green xylene cyanol FF in 100 ml
water OR 0 · 1 g ready-mixed
indicator in 100 ml water

Methyl red Red to yellow 4-4-6-0 0 1 g indicator in 100 ml

ethyl alcohol/water, 3:2

(COOH) 2, Phenolphthalein Colourless to 8-4-10-0 0-1 g indicator in 100 ml

Weak acid (CH 2COOH) 2, pink ethyl alcohol/water, 3:2
and CH3COOH,
strong base C 6H 4(COO) 2HK
(as above)

Weak acid
and No indicator
weak base

27
28 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

the eye is very sensitive to changes in grey tones, a sharp end-

point is obtained with this indicator.
Many indicators are available, the commonest in use by
beginners being those mentioned on p . 27.

Determination of the concentration of a solution of

sodium hydroxide, given oxalic acid crystals, with sub-
sequent determination of the concentration of a solution
of hydrochloric acid
(A) Using oxalic acid

Requirements
Volumetric analysis apparatus, including a 250 ml graduated
flask and clock glass or weighing bottle.
Oxalic acid dihydrate crystals.
Caustic soda, preferably in pellet form.
Concentrated hydrochloric acid.
Phenolphthalein indicator solution.

To prepare an approximately decinormal oxalic acid solution.

Oxalic acid dihydrate has the formula ( C O O H ) 2 - 2 H 2 0 and has
two hydrogen atoms replaceable by a metal:

(COOH)2 + 2NaOH = (COONa)2 + 2 H 2 0

or
( C O O H ) 2 + 2 N a + + 2 0 H " -+ (COO)5~ + 2 N a + + 2 H 2 0 .
Hence a normal solution contains half the molecular weight in
grams in one litre of solution.
· ι . · u. ( C 0 0 H ) 2- 2 H 20 12607 „
Equivalent weight = ^ — = — - — = 63-04.M

To prepare an approximately decinormal solution of sodium

hydroxide. The equivalent weight of sodium hydroxide is 40-00,
 ACID-BASE TITRATIONS 29
thus an approximately 0-1 Ν solution may be prepared by dis-
solving 4 g in 1000 ml solution. Caustic soda is a very deliquescent
substance and so cannot be weighed out accurately, also it is very
corrosive and should be handled carefully and not touched with
the fingers. A rough balance is advisable. Use a clock glass to
weigh out approximately 4 g and dissolve in 200 ml (preferably)
carbon dioxide-free distilled water (water which has been boiled
to drive out dissolved carbon dioxide and then placed in a stop-
pered container). Cool the solution, if necessary, and pour into a
container and add 800 ml more carbon dioxide-free distilled
water. Stopper the bottle firmly or store in an aspirator-type
container with a bulb tube of soda-lime in its one-holed rubber
bung.

Method
1. Weigh accurately between 1-4 and 1-6 g oxalic acid crystals,
using a weighing bottle or a clock-glass. Details of method are
on p. 6.
2. Dissolve the crystals in distilled water, transfer the solution to
a 250 ml standard flask and make the solution u p to the mark.
3. Pipette 25 ml portions of the sodium hydroxide solution into
three (or four) conical flasks. Add two drops Phenolphthalein
indicator solution.
4. Add the oxalic acid solution from the burette until the end-
point is reached. This is when the addition of a drop of acid
first causes the pink colour to disappear. Take careful burette
readings.

Calculation
See worked example on p. 31.

(B) Using hydrochloric acid

To prepare an approximately decinormal solution of hydro-

chloric acid. Concentrated hydrochloric acid contains about 3 5 %
30 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

hydrogen chloride (wt./wt.) and thus its equivalent weight of

36-46, when expressed in grams, is present in approximately 100 g
of the concentrated acid. The specific gravity of concentrated
hydrochloric acid is 1-18 and thus 8-5 ml concentrated acid,
when diluted to one litre of solution gives an approximately
0-1 Ν solution.
Measure 8-5 ml concentrated hydrochloric acid, using a 10 ml
measuring cylinder and pour into a beaker containing 200 ml
water. Stir and pour the solution into a container and add 800 ml
more water.

Method
As (3) and (4) above, but substituting hydrochloric acid for
oxalic acid :

N a O H + HCl = NaCl + H 2 0
N a O H = HCl = 1 equivalent.

Hence a normal solution of hydrochloric acid contains the gram

molecular weight, 36-46 g, dissolved in 1000 ml solution.

Calculation
Calculate the normality and hence concentration of the acid
from the titration results and the determined normality of the
alkali solution.

Writing-up of titrimetric determinations

An example of reporting the first determination of the

previous exercise
Weight of weighing bottle and oxalic acid crystals = 13-442 g
Weight of weighing bottle = 11-922 g
Weight of oxalic acid crystals = 1-520 g
 ACID-BASE TITRATIONS 31
Titrations
Volume of sodium hydroxide solution = 25-00 ml (give pipette
volume after any calibration correction has been made).
Burette readings of volumes of oxalic acid solution :

1 (approx.
titration) 2 3 4

2nd reading 27-80 26-40 28-45 26-40

1st reading 1-00 0 00 2-00 0 00

26-80 ml 26-40 ml 26-45 ml 26-40 ml

Therefore, average volume of oxalic acid solution needed to

neutralize 25 ml sodium hydroxide solution is 26-42 ml. (Give
burette calibration correction, if necessary.)

(COOH)2 + 2NaOH = (COONa)2 + 2 H 20 .

( C O O H ) 2 = 2 N a O H = 2 equivalents.
(COOH)2 ^ N a QH ξ J equivalent.

Molecular weight of oxalic acid crystals, ( C O O H ) 2 * 2 H 2 0 , is

126-07. Therefore equivalent weight of oxalic acid crystals is
63-04.

63-04 g oxalic acid crystals in 1000 ml solution gives a Ν

solution. Therefore 1-520 g oxalic acid in 250 mlf solution gives

1-52 χ 1000\
Ν solution
63-04 χ 2 5 0 /
= 0-09645 Ν .

By titration, 26-42 ml 0-09645 Ν oxalic acid neutralizes 25-00 ml

sodium hydroxide solution

Ν χ V\ = N2V2

t Give corrected volume of the flask, if necessary.

c
32 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

where N\, N2 and V\, V2 are the normalities and volumes of the
first and second solutions.
26-42 ml 0-09645 Ν acid = 25-00 ml * Ν alkali.
Therefore normality of the sodium hydroxide solution, x,

= 0-1020 N .
One litre of Ν sodium hydroxide solution contains 40-00 g
sodium hydroxide.
Therefore one litre of 0-102 Ν sodium hydroxide solution
contains (40-00 χ 0-102) g
= 4-08 g sodium hydroxide (correct to two places of decimals).

An alternative method of calculation, employing moles

Weight of oxalic acid crystals, ( C O O H ) 2 - 2 H 2 0 , in 250 ml
solution = 1 -520 g. Therefore number of moles in 1 ml of solution

where 126-07 is the mol.wt. of oxalic acid crystals.

By titration, 26-42 ml oxalic acid solution neutralizes 25-00 ml
sodium hydroxide solution.
Moles of oxalic acid in 26-42 ml solution
1-52 X 26-42
126-07 χ 250
Inspection of the equation for the reaction,
(COOH)2 + 2NaOH = (COONa)2 + 2 H 20 ,
shows that (COOH)2 Ξ 2NaOH.
Therefore moles of sodium hydroxide in 25 ml solution
_ / 2 x 1-52 χ 26-42\
" V 126-07 χ 250 )
 ACID-BASE TITRATIONS 33

Hence moles of sodium hydroxide in 1000 ml solution

_ (2 χ 1-52 χ 26-42 χ 1000\
" V 126-07 χ 250 χ 25 /
= 0-1019.
One mole of sodium hydroxide = 40-00 g
Therefore, 0-1019 moles sodium hydroxide = (40-00 χ 0-1019)
= 4-076 g .
Concentration of the sodium hydroxide solution is 4-08 g per litre
(correct to two places of decimals).

Standardization of a solution of sulphuric acid using borax

and subsequent checking of the result using anhydrous
sodium carbonate
(A) Using borax

Requirements
Borax crystals.
Anhydrous sodium carbonate, previously dried in an oven at
270-300°C for an hour and allowed to cool in a desiccator. (If no
oven is available, place about 2 g of the carbonate in an evapora-
ting basin and heat for 10 min on a sand-bath, stirring with a
glass rod. Allow to cool in a desiccator.)
Concentrated sulphuric acid.
Screened methyl orange indicator solution.

To prepare an approximately decinormal solution of borax.

Borax has the formula N a 2 B 4 0 7 - 1 0 H 2 O , and reacts with
sulphuric acid as follows :
N a 2B 40 7 + H 2S 0 4 + 5 H 20 = N a 2S 0 4 + 4 H 3B 0 3;
alternatively,
2
( B 4 0 7 ) ~ + 2 H + + 5 H 2 0 -> 4 H 3 B 0 3
N a 2 B 4 0 7 = H 2 S 0 4 = 2 equivalents.
34 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Molecular weight of borax (decahydrate) is 381-4. Therefore

equivalent weight of borax is

The boric acid, H3BO3, formed in the reaction, is too weak an

acid to interfere with the titration result.
Weigh out accurately between 4-6 and 4-9 g borax. W a r m to
dissolve, since borax is very slow to dissolve in cold water,
transfer the cooled solution to a 250 ml standard flask and make
up to the mark. Calculate the exact normality of the solution. A
more accurate procedure is to weigh out accurately about 0-5 g
quantities of borax into three or four conical flasks, dissolve and
titrate directly.

To prepare an approximately decinormal solution of sulphuric

acid. The specific gravity of concentrated sulphuric acid is 1-84
and therefore 49 g (the gram equivalent weight) occupies a little
over 27 ml. Measure 3-0 ml concentrated sulphuric acid, using a
small measuring cylinder and pour it carefully into a beaker
containing about 200 ml water. Stir and then pour into a container
and add 800 ml water.

Method
1. Place the sulphuric acid solution in the burette and 25 ml
aliquots of the borax solution in the flasks.
2. A d d two drops screened methyl orange indicator. This indi-
cator gives a violet colour in acid solution, a green colour in
alkaline solution and a bluish-grey colour at the end-point.
3. Titrate in the usual way.

(B) Using sodium carbonate

To prepare an approximately decinormal solution of sodium
carbonate. The reaction between sodium carbonate and sulphuric
 ACID-BASE TITRATIONS 35
acid may be represented:

N a 2C 0 3 + H 2S 0 4 = Na2S04 + H 20 + C 0 2
N a 2 C 0 3 Ξ H 2 S 0 4 = 2 equivalents.

Therefore equivalent weight of sodium carbonate is

Hence 250 ml 0-100 Ν sodium carbonate solution requires 1-325 g

of the salt.

Method
1. Weigh accurately between 1-2 and 1-4 g of the dried salt,
using a stoppered bottle (not a clock glass).
2. Dissolve the carbonate in about 100 ml distilled water, transfer
to a 250 ml volumetric flask, make the volume up to the mark
and shake thoroughly.
3. Pipette 25 ml aliquots into the conical flasks, wash down with
distilled water and add two or three drops screened methyl
orange indicator, titrate as before.

Calculation
From the calculated normalities of t h e solutions of borax and
sodium carbonate and from the titration results, calculate the
normality of the sulphuric acid. Use this normality to determine
the concentration of the sulphuric acid solution.

Equivalent weight H 2 S 0 4 = 49*04.

Acidic primary standards

The common mineral acids cannot easily be obtained in the
pure state and organic substances are usually used to standardize
alkaline solutions. Succinic acid, ( C H 2 C O O H ) 2 , may be used
instead of oxalic acid.
36 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

C H 2C O O H C H 2C O O "
+
I + 2Na + 2 0 H " -> | + 2Na+ + 2H20
C H 2C O O H C H 2C O O "
Thus i ( C H 2 C O O H ) 2 = N a O H = 1 equivalent,

and a normal solution of succinic acid contains half the molecular

weight expressed in grams, that is, (118-09/2) = 59-05 g per litre
of solution. Benzoic acid, C 6 H 5 C O O H , may also be used, the
method is given on p . 51.
One of the most highly recommended substances is potassium
hydrogen phthalate, C 6 H 4 · C O O H COOK. To ensure complete
drying, it should be dried in an oven at 100-150°C:

r r ^ N COOH r r ^ X COO - N a +
+ Na++OH--> +H20.
L
V^COO"K+ \^XOO~K +
The equivalent weight of this acidic salt is 204-23. Its solution
should not be kept longer than six weeks because it is liable to
become contaminated with moulds; shaking at regular intervals
helps to prevent this. Sulphamic acid, N H 2 S 0 3 H , is recommended
as a primary standard :
N H 2 S 0 3 H + N a + + O H " -> N H 2 S 0 3 " + N a + + H 2 0 .
An inorganic acid, which is used as a primary standard, is
constant boiling hydrochloric acid. It is prepared as follows. Dilute
250 ml concentrated hydrochloric acid with 250 ml water and put
in a 1000 ml distillation flask; fit the latter with a condenser and a
200°C or 360°C thermometer. Heat the solution, discarding the
first 250 ml of distillate. By this time, the temperature of the
boiling acid solution should have been steady for some while,
showing that a constant boiling mixture is now present in the
flask and its mixed vapour has a constant composition. The
composition depends on the barometric pressure which must now
be read. Collect 20-30 ml of the distillate in a clean dry receiver.
To obtain a standard solution, weigh accurately 4-4-4-6 g of the
acid in a stoppered weighing bottle. Transfer the solution to a
 ACID—BASE TITRATIONS 37

Composition of constant boiling hydrochloric acid/water mixture in grams

Composition, Weight of solution

Pressure, % hydrochloric in g to contain 1
mm of mercury acid (wt./wt.) mole hydrochloric acid

730 20-293 179-555

740 20-269 179-766
750 20-245 179-979
760 20-221 180-193
770 20-197 180-407

250 ml graduated flask, rinsing the bottle well and transferring

all rinsings to the flask. Then make the solution u p to the mark.
Calculate the exact normality or molarity from the weight taken
and the data above.
The constant boiling hydrochloric acid may be kept as a reliable
standard, provided it is well stoppered. Storage should be in a
dark or ill-lit place as hydrochloric acid shows slight photo-
chemical oxidation to chlorine and water.

Equivalent weight HCl = 3 6 4 6 .

DETERMINATIONS USING STANDARD ACID

OR STANDARD ALKALI SOLUTIONS
I. DETERMINATION OF PERCENTAGE WATER LOST FROM A
SAMPLE OF WASHING SODA CRYSTALS BY EFFLORESCENCE

Washing soda crystals, N a 2 C 0 3 - 1 0 H 2 O , soon lose water of

crystallization on exposure to the air.

Requirements
Partially effloresced washing soda crystals.
Standardized 0 1 Ν (0-05 M) sulphuric or 0 1 Ν (0-1 M) hydro-
chloric acid.
Screened methyl orange indicator solution.
38 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Method
1. Weigh out accurately about 3 g of the washing soda sample.
2. Dissolve in water, transfer the solution to a 250 ml graduated
flask and make up to the mark.
3. Pipette out 25 ml aliquots and add two or three drops screened
methyl orange indicator to each.
4. Titrate with standardized 0-1 Ν acid, as in previous deter-
mination.

Example of a calculation from an actual determination

Weight of effloresced washing soda taken = 2-696 g
Average volume of 0-104 Ν sulphuric acid required to
react with 25-00 ml aliquot sodium carbonate = 20-60 ml

N a 2 C O 3 1 0 H 2 O + H 2 S 0 4 = N a 2 S 0 4 + C 0 2 + 1 1 H 20 .

Hence N a 2 C 0 3 · 1 0 H 2 O ΞΞ H 2 S 0 4 = 2 equivalents.

Therefore the equivalent weight of washing soda

_ mol.wt. N a 2 C O 3 - 1 0 H 2 O
2
286-14
2
= 143-1.

By titration:
20-60 ml 0-104 Ν sulphuric acid ΞΞ 25-00 ml χ Ν sodium car-
bonate solution

0-0857 Ν χ .
 ACID-BASE TITRATIONS 39

Now 1 0 0 0 ml Ι Ό Ο Ν solution of washing soda contains 143-1 g.

Therefore, 2 5 0 ml 0 - 0 8 5 7 Ν solution of washing soda contains

= 3 - 0 6 6 g per litre.

But the solution was made by dissolving 2 - 6 9 6 g in 2 5 0 ml

solution.

Percentage loss in weight

= (3-066 - 2-696) χ 100

3-066

= 12-1 (correct t o one decimal place).

II. DETERMINATION OF THE RATIO OF Χ TO y I N

x N a 2 C 0 3 - v N a H C 0 3 - 2 H 2 0 , SODIUM SESQUICARBONATE

Sodium sesquicarbonate behaves as though it is an intimate

mixture of sodium carbonate a n d sodium bicarbonate, in mole-
cular proportions. If the solution is titrated with acid, the
"half neutralization" point of the sodium carbonate, e.g.

N a 2 C 0 3 + HCl = N a H C 0 3 + H 2 0 ,

is shown by the indicator Phenolphthalein giving the pink-

colourless change. If methyl orange indicator is now added to the
solution, it will give its colour change when all the sodium
bicarbonate has reacted with the acid,

N a H C 0 3 + HCl = NaCl + H 2 0 .

The volume of acid needed for the first of these chemical changes,
a ml, is exactly the same as that required for the second change,
in respect of the original sodium carbonate present. The acid, in
addition to 2a ml, which is required to reach the second end-point,
40 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

is used in reacting with the bicarbonate present in the original

solid. Explained diagrammatically:

N a 2 C 0 3 A N a H C 0 3 4 NaCl

N a H C 0 3 Λ NaCl
(present in
original salt)
where a and b represent millilitres of acid required for reactions
and 2a + b is the total volume of acid needed.

Requirements
Sodium sesquicarbonate crystals.
Approximately 0 1 Ν hydrochloric acid or sulphuric acid.
Phenolphthalein indicator solution.
Screened methyl orange indicator solution.

Method
1. Weigh out roughly 3 g sodium sesquicarbonate crystals and
dissolve in approximately 250 ml solution.
2. Take a 25 ml portion. A measuring cylinder may be used. A d d
two drops Phenolphthalein indicator.
3. Titrate with the acid, noting volume required to first render
the solution very pale pink.
4. To the practically colourless solution, add two drops screened
methyl orange indicator. Add the acid until the green solution
becomes grey-violet. Read the burette carefully.

Calculation
If a represents millilitres of acid required for the first end-point,
then the total number of millilitres of acid required may be
represented by 2a + b. Calculate the value of b. The ratio of a
to b is as χ to y in the formula
x N a 2C 0 3 ^ N a H C 0 3 · 2 Η 20 .
 ACID-BASE TITRATIONS 41

I I I . DETERMINATION OF THE CONCENTRATION OF SODIUM

HYDROXIDE AND SODIUM CARBONATE IN A SOLUTION OF
BOTH THESE SUBSTANCES

In the first stage of this titration, which is shown by the indicator

Phenolphthalein changing from pink to colourless, the sodium
hydroxide is converted into sodium chloride and the sodium
carbonate is converted into sodium bicarbonate.
N a O H + HCl = N a C l + H 2 0
and N a 2 C 0 3 + HCl = N a C l + N a H C 0 3 .
Methyl orange gives an alkaline reaction with sodium bicarbonate
and will show the end-point when all the bicarbonate is converted
to chloride,
N a H C 0 3 + HCl = NaCl + C 0 2 + H 2 0 .
If χ ml acid gives the end-point with Phenolphthalein and a further
y ml acid gives the end-point with methyl orange, then the volume
reacting with all the sodium carbonate is 2y ml and the volume
reacting with the sodium hydroxide is χ — y.

Requirements
Sodium hydroxide.
Anhydrous sodium carbonate.
Standardized hydrochloric or sulphuric acid, approximately
0-1 N .
Phenolphthalein indicator solution.
Screened methyl orange indicator solution.

Method
1. Prepare 250 ml of a solution which is approximately 0*1 Ν
with respect to both sodium hydroxide and sodium carbonate
(see pp. 28 and 34).
2. Take 25 ml aliquots of this solution and titrate against the
hydrochloric (or sulphuric) acid of known normality, using
42 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Phenolphthalein indicator until the first drop of acid turns the

solution colourless. Take careful reading.
3. Add two drops screened methyl orange indicator and titrate
to the next end-point.

Example of a calculation
Volume of mixed sodium hydroxide and sodium
carbonate solution taken = 25*00 ml
Volume of 0*100 Ν acid required for neutralization
using Phenolphthalein as the indicator = 24*00 ml
Volume of additional acid required for neutralization
when screened methyl orange indicator added = 5*00 ml

Volume of 0*100 Ν acid needed to neutralize half the

carbonate present in 25 ml solution = 5*00 ml
Therefore volume of 0-100 Ν acid needed to neutralize
all the carbonate in 25 ml solution = 10 ml

10*00 ml 0*100 Ν acid Ξ 25*00 ml χ Ν carbonate

'10*00 χ 0·10\ Λ Μ
Γ

= 0*04 Ν
25 )
2HC1 + N a 2 C 0 3 - 2NaCl + H 2 0 + C 0 2 .

Hence

m o l e c u , r
equivalent weight N a 2 C 0 3 = ^ * * * * * = 53-00.

Thus 0*04 Ν sodium carbonate contains (0*04 X 53*00) g per litre

= 2*12 g per litre.

Volume of 0*100 Ν acid needed to neutralize both carbonate and

hydroxide - (24*00 + 5*00) = 29*00 ml
Volume of 0*100 Ν acid needed to neutralize hydroxide only =
(29*00 - 10*00) = 19 00 ml
 ACID-BASE TITRATIONS 43

19-00 ml 0-100 Ν acid = 20-00 ml y Ν hydroxide

19-00 Χ 0 · 1 0 0 \ .0 0 9 5N

20 )
HCl + N a O H = NaCl + H 2 0 .
Hence
equivalent weight N a O H = molecular weight = 40-00.

Thus 0-095 Ν sodium hydroxide contains (0-095 X 40-00) g per

litre
= 3-80 g per litre.

I V . DETERMINATION OF THE PERCENTAGE AMMONIA IN AN

AMMONIUM SALT BY T W O DIFFERENT METHODS

Method I
A m m o n i u m compounds react with sodium hydroxide to give
ammonia and the appropriate sodium salt in solution, e.g.

N H 4C 1 + N a O H = N H 3 + NaCl + H 2 0 .

Excess sodium hydroxide solution, of known normality, is

added to a known weight of the salt, or to a solution of the salt
and the solution is then boiled to drive off the ammonia produced.
The remaining sodium hydroxide may be found by titration with
acid of known normality and thus the sodium hydroxide converted
to sodium salt may be calculated by difference. This type of
titration is called a "back titration". The sodium hydroxide
removed by the reaction is equivalent to the ammonia evolved
and hence the weight of this ammonia may be calculated.

Requirements
Ammonium salt, e.g. ammonium chloride, ammonium sulphate.
0-1 Ν sodium hydroxide of known factor (the factor is the
fraction by which the solution differs from 1 Ν or 1 M).
0-1 Ν hydrochloric or sulphuric acid of known factor.
44 TÏTRIMETRIC AND GRAVIMETRIC ANALYSIS

Purchased ampoules of concentrated solutions of the alkali and

the acid, which, on correct dilution, give exactly decinormal
solutions, are useful for this type of determination.

Method
1. Weigh out accurately between 1-2 and 1-4 g ammonium
chloride or 1-6 and 1-8 g ammonium sulphate, dissolve and
make up to 250 ml solution in a graduated flask.
2. Into three or four flasks, place 25 ml aliquots of the ammonium
salt solution.
3. Add exactly 50-00 ml standardized decinormal sodium hydrox-
ide solution to each flask. Boil the solution gently for 15 min,
placing a funnel in the neck of the flask to avoid loss of solution
as spray.
4. Rinse both sides of the funnel, allowing the rinsings to drain
into the flask. Add two drops Phenolphthalein indicator.
5. Titrate with standardized decinormal hydrochloric or sulphuric
acid until a drop first turns the pink solution colourless.

Example of a calculation from an actual determination

Weight of ammonium salt dissolved in 250 ml solution = 1 -202 g
Average volume of 0-120 Ν hydrochloric acid required
to neutralize 25 ml aliquot and the added 50-00 ml
0-100 Ν sodium hydroxide = 23-25 ml

NaOH + N H 4X = N H 3 + NaX + H 2 0
N a O H = N H 3 = 1 equivalent.

Hence the equivalent weight of ammonia = molecular weight of

ammonia = 17-03.

By titration:
The excess 0-100 Ν alkali solution is equivalent to 23-25 ml
0-120 Ν hydrochloric acid. To calculate the volume of acid needed
 ACID-BASE TITRATIONS 45

if it had the same normality as the alkali:

23-25 ml 0-12 Ν acid ΞΞ χ ml 0-100 Ν alkali

/23·25 Χ 0 · 1 2 \ ml

V o-io Γ
= 27-90 ml.
Volume 0-100 Ν sodium hydroxide solution used in reaction with
the ammonium salt
= (50-00 - 27-90) ml
= 22-10 ml.

Since 1000 ml 0-100 Ν sodium hydroxide is equivalent to 1-703 g

ammonia, then 22*10 ml 0-100 Ν sodium hydroxide is equivalent
to
Ί - 7 0 3 X 22-10\
1000 ι g ammonia
= 0-03764 g ammonia.

Hence weight of ammonia obtainable from 250 ml solution

= (10 X 0-03764) g
= 0-3764 g.
Percentage ammonia in salt
= /0-3764 Χ 100\
l original weight J
\ of salt taken /
/0-3764 Χ 100\
V 1-202 j
= 31-32
= 31-3 (correct to one place of decimals).
The given salt was in fact, ammonium chloride. Theoretically
the percentage of ammonia in ammonium chloride is 31-84. It is
recognized that results by this method are low.f
f Quantitative inorganic Analysis, by R. Belcher and A. J. Nutten, 2nd ed.,
p. 192.
46 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Method II
When formaldehyde is added to ammonium salts of strong acids,
hexamethylenetetramine (hexamine) and free acid are formed.
For example :

6 H C H O + 4 N H 4 C 1 = C 6 H 1 2 N 4 + 6 H 2 0 + 4HC1.

The solution may be titrated in exactly the same way as a hydro-

chloric acid solution. The hexamethylenetetramine is too weak a
base to cause interference.

Requirements
Ammonium chloride or sulphate crystals.
4 0 % formaldehyde solution (formalin).
Standardized 0-1 Ν sodium hydroxide solution.

Method
1. Weigh out accurately between 1-2 and 1-8 g ammonium
chloride or ammonium sulphate, dissolve in distilled water and
make up to the mark in a 250 ml volumetric flask.
2. Neutralize the formalin by adding a drop of Phenolphthalein
indicator followed by 0-1 Ν sodium hydroxide, drop by drop,
until the solution is coloured pale pink.
3. Pipette 25 ml aliquots of the ammonium salt solution into
three or four conical flasks.
4. To each flask add 5 ml of the neutralized formaldehyde
solution and two drops of Phenolphthalein solution.
5. The reaction is not instantaneous, therefore the flasks must be
allowed to stand for 2 min.
6. Titrate with the standardized 0-1 Ν sodium hydroxide solution
until a drop first colours the solution pale pink.

Calculation
F r o m the equation above and from the equation for the reaction
 ACID—BASE TITRATIONS 47

between hydrochloric acid and sodium hydroxide, it is seen that

NH4CI s N H 3 = H C l = N a O H = 1 equivalent.
Hence the number of gram-equivalents of sodium hydroxide used
in the titration is equivalent to the number of gram-equivalents of
ammonium ion in the conical flask. The equivalent weight of
ammonia is 17-03, hence calculate the percentage ammonia in the
salt.
This method gives excellent results.

V . DETERMINATION OF THE SOLUBILITY OF CALCIUM

HYDROXIDE"f
Calcium hydroxide is only sparingly soluble in water, so its
solubility may be determined by titration with acid. Calcium
hydroxide is a strong base, therefore any acid-base indicator may
be selected.

Requirements
Slaked lime (milk of lime).
Standardized 0-1 Ν hydrochloric acid.
Phenolphthalein indicator solution.
500 ml stoppered bottle.

Method
1. Shake excess calcium hydroxide with approximately 300 ml
distilled water in a 500 ml stoppered bottle at frequent intervals
for a period of 15 min.
2. Filter off the excess solid.
3. Pipette two 25 ml portions of the filtrate into each conical
flask and add a few drops Phenolphthalein indicator.
4. Titrate the solution with the standardized 0-1 Ν hydrochloric
acid.
t The solubility product of calcium hydroxide may also be determined by
titrimetry. See Introductory Practical Physical Chemistry, by D . Τ. Burns and
Ε. M. Rattenbury.
48 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Example of a calculation from an actual determination, at 20°C.

Volume 0-100 Ν hydrochloric acid required to react with 50-00 ml
saturated calcium hydroxide solution = 23-50 ml

C a ( O H ) 2 + 2HC1 = C a C l 2 + 2 H 2 0 .
Hence C a ( O H ) 2 = 2HC1 = 2 equivalents.
Thus a normal solution of calcium hydroxide contains half the
gram molecular weight = 74-095/2 = 37-048 g per litre of
solution.

By titration:
23-50 ml 0-100 Ν hydrochloric acid
= 50-00 ml χ Ν calcium hydroxide

= 0-0470 N .

Concentration of a 0-0470 Ν calcium hydroxide solution

= (0-047 X 37-048) g per litre

= 1 -742 g per litre.
Thus a saturated solution of calcium hydroxide, at 20°C, contains
1-74 g per litre of solution.

To express the solubility as grams per 1000 g water and assum-

ing the volume of dissolved hydroxide to be negligible:
At 20°C the specific gravity of water = 0-9982.

Thus 998-2 g water dissolves 1 -742 g calcium hydroxide. Therefore

1000 g water dissolves ( LZl?_2i_1222 ] g calcium hydroxide

\ 998-2 /
= l-745g.
Solubility of calcium hydroxide = 1 -75 g per 1000 g water at 20°C.
 ACID-BASE TITRATIONS 49

V I . DETERMINATION OF THE EQUIVALENT WEIGHT OF

ORGANIC ACIDS BY TITRATION W I T H ALKALI SOLUTION

Barium hydroxide is a strong base which has an advantage over

sodium hydroxide in the titration of weak acids.

Preparation of an approximately decinormal solution of

barium hydroxide
Sodium hydroxide absorbs carbon dioxide from the atmosphere
and a weak acid may not be sufficiently acidic in character to
disrupt the sodium carbonate in the solution: hence more than
the correct volume of sodium hydroxide solution is required to
reach the equivalence point, thus giving inaccurate results for
the acid concentration. Barium hydroxide also absorbs atmos-
pheric carbon dioxide but dense insoluble barium carbonate sinks
to the bottom of the container. Barium hydroxide is an unusual

FIG. 10. Container of barium hydroxide solution.

50 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

hydroxide in so far that it exists as a well-defined octahydrate,

B a ( O H ) 2- 8 H 20 .
Weigh out 15 g barium hydroxide octahydrate, dissolve in one 1.
water. Allow to stand for 48 hr, then decant or filter off the clear
solution from the settled barium carbonate, just before use.
It must, of course, be standardized each time it is used. Potassium
hydrogen phthalate, succinic acid or benzoic acid may be used for
standardization. Barium hydroxide solution may be covered with
a layer of oil (e.g. liquid paraffin) to prevent the entry of carbon
dioxide and the container stoppered with a bung containing a
delivery tube through which the solution is siphoned off*. The
equation for the reaction between barium hydroxide and an acid
(e.g. acetic acid) is:
B a ( O H ) 2 + 2 C H 3C O O H = ( C H 3C O O ) 2B a + 2 H 2 0
B a ( O H ) 2 Ξ 2CH3COOH ΞΞ 2 equivalents.
Hence a normal solution of barium hydroxide contains half the
molecular weight expressed in grams per litre of solution.
Equivalent weight B a ( O H ) 2 - 8 H 2 0 = 157-74 .

Examples of organic acids for the determination. Organic acids

whose equivalent weights in neutralization reactions may be
determined are oxalic, succinic, tartaric, benzoic and salicylic
acids. The last two acids are not sufficiently soluble in water to be
used in entirely aqueous solution and are dissolved in alcohol/
water mixtures.

Requirements
Solid organic acid (see above).
Standardized 0-1 Ν barium or sodium hydroxide.
Phenolphthalein indicator solution.

Method
1. Weigh out accurately 1-4-1-6 g oxalic acid dihydrate, or
1-4-1-6 g succinic acid, or 1-8-2-0 g tartaric acid, dissolve in
 ACID-BASE TITRATIONS 51

water and make up to 250 ml solution in a standard flask. In

the case of benzoic acid or salicylic acid, weigh out accurately
three portions of about 0-4 g into each of three conical flasks
and add 15 ml ethyl alcohol to each.
2. Take 25 ml aliquots of the water-soluble acids. Titrate the
alcohol-soluble acids directly.
3. Add two drops Phenolphthalein and titrate with the standard-
ized 0-1 Ν alkali.

Calculation
Calculate the normality of the acid solution, e.g.

24-50 ml 0-11 Ν barium hydroxide solution

Ξ 25-00 ml χ Ν acid solution

Hence

This calculated normality is given by the weight of acid dissolved

in 250 ml solution, hence calculate the weight needed to give
1000 ml 1-00 Ν solution.

Use of benzoic acid for standardizing solutions of alkalis

Benzoic acid, dissolved in alcohol, is suitable for standardizing
solutions of alkalis.

Example of a calculation of determination of normality of

an alkali solution, given benzoic acid crystals
Weight of benzoic acid dissolved in 15-0 ml alcohol
in conical flask = 0-4113 g
Volume of χ Ν sodium hydroxide solution required
to neutralize 15-0 ml of the alcohol (the " b l a n k "
titration) = 0-10 ml
52 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Volume of χ Ν sodium hydroxide solution required

to react with the benzoic acid = (33-95-0-1)
= 33-85 ml
C 6 H 5 C O O H + Na+ + O H "
-> C 6 H 5 C O O - + N a + + H 2 0 .
Hence C 6 H 5 - C O O H = N a O H ΞΞ 1 equivalent.
Thus a normal solution of benzoic acid contains the gram mole-
cular weight, i.e. 122-1 g dissolved in o n e l . of solution.

33-85 ml χ Ν sodium hydroxide ΞΞ 0-4113 g benzoic acid.

Also
1000 ml 1 -0 Ν sodium hydroxide ΞΞ 122-1 g benzoic acid.

122-1 g benzoic acid reacts with exactly 1000 ml 1 -00 Ν hydroxide

solution sodium.
Therefore 0-4113 g benzoic acid reacts with exactly 33-85 ml of
/1000 X 0-4113\
N
\33-85 X 1 2 2 - 1 /
= 0-09951 Ν sodium hydroxide solution.
Hence normality of the sodium hydroxide solution is 0-100 N,
correct to three places of decimals.
Equivalent weight oxalic acid, ( C O O H ) 2 - 2 H 2 0 = 63 04
succinic acid, ( C H 2 · C O O H ) 2 = 59-05
tartaric acid, (CH · O H · C O O H ) 2 - 7 5 - 0 4
benzoic acid, C 6 H 5 - C O O H = 122-13
salicylic acid, C 6 H 4 · C O O H - O H = 1 3 8 - 1 3

V I I . DETERMINATION OF THE EQUIVALENT WEIGHT OF

CERTAIN METALS
The equivalent weight of metals which dissolve readily in dilute
mineral acid may be determined fairly accurately by finding the
exact quantity of acid needed to react with a known weight of
 ACID-BASE TITRATIONS 53

metal. Magnesium, zinc and freshly purchased calcium (i.e. cal-

cium which is not grossly oxidized) may be used.

Requirements
Metal (see above).
Standardized 1-0 Ν hydrochloric acid or standardized 1-0 Ν
sulphuric acid (the latter is unsuitable for calcium).
Standardized 0*1 Ν sodium hydroxide.
Phenolphthalein indicator solution.
500 ml beaker.

Method
1. Weigh out accurately 0-65-0-85 g of zinc (granulated or dust)
or 0-25-0-35 g magnesium or 0-35-0-55 g calcium. Use the
"weighing by difference" method, tipping the metal into a
500 ml beaker.
2. Add exactly 50-00 ml acid, using a burette. In the case of zinc,
warming and/or the addition of a few drops copper sulphate
solution as catalyst may be necessary for the reaction to be
completed.
3. Transfer the solution to a 250 ml standard flask, with thorough
rinsing. Transfer the rinsings, also. Make up to the mark.
4. Take 25 ml aliquots and titrate with standardized 0-1 Ν
sodium hydroxide using Phenolphthalein as indicator.

Example of a calculation from an actual determination

Weight of magnesium = 0-258 g
Average volume 0-100 N sodium hydroxide
required to neutralize 25-00 ml aliquot = 28-95 ml

Mg + 2HC1 = M g C l 2 + H 2
Normality of acid used to dissolve magnesium = 1Ό0 Ν
54 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Normality of 50-00 ml acid after solution made

up to the mark in 250 ml flask (disregarding
the reaction) - 0-20 Ν
Hence acid present in 25 ml aliquot = 25 ml of 0-20 Ν
ΞΞ 50 ml of 0-10 Ν

By titration:
The excess 0-20 Ν hydrochloric acid is equivalent to 28-95 ml
0-10 Ν sodium hydroxide.
Therefore the volume 0-10 Ν hydrochloric acid used in reaction
with magnesium
= (50-0-28-95) = 21-05 ml.
Thus 21-05 ml 0-10 Ν acid are equivalent to one-tenth weight of
magnesium taken.
Hence 1000 ml 1-0 Ν acid are equivalent to

/Ο-0258 χ ΙΟΟΟλ
g magnesium
V 21-05 χ 0-1
= 12-26 g.
Therefore equivalent weight of magnesium is 12-3.

The correct value for the equivalent weight of magnesium,

when it reacts with acids, is 12-16.

Vlll. DETERMINATION OF THE EQUIVALENT WEIGHT OF

CERTAIN CARBONATES
The equivalent weight of insoluble, normal carbonates may be
estimated by determining the exact quantity of acid needed to
react with a known weight of the carbonate. The carbonates of
the alkaline earth metals (the normal, not the basic carbonate of
magnesium) and lithium carbonate are suited to this method.
 ACID—BASE TITRATIONS 55
Requirements
Insoluble carbonate (see above).
Standardized 1 Ό Ν hydrochloric acid.
Standardized 0 - 1 Ν sodium hydroxide.
Screened methyl orange indicator solution.

Method
1. Weigh out accurately 1 - 2 - 1 -4 g calcium carbonate (precipitated
chalk) or 0 - 7 - 0 - 9 g lithium carbonate or 2 - 4 - 2 - 6 g barium
carbonate, etc. Use the method of weighing "by difference"
and tip the substance into a 5 0 0 ml beaker.
2 . Add exactly 5 0 - 0 0 ml 1-0 Ν hydrochloric acid, using a burette.
3 . Transfer the solution to a 2 5 0 ml standard flask, with thorough
rinsing and make the solution u p to the mark.
4 . Take 2 5 ml aliquots and titrate with standardized 0 - 1 Ν
sodium hydroxide. Add two drops screened methyl orange
indicator and titrate as usual. Alternatively, if the carbon
dioxide is expelled by boiling the solution, the titration is that
of a strong acid-strong base and any indicator will give a
correct result.

Example of a calculation from an actual determination

Weight of lithium carbonate = 0-730 g
Average volume of 0 - 1 0 0 Ν sodium hydroxide
required to neutralize 2 5 - 0 0 ml aliquot = 3 0 - 3 0 ml

L i 2 C 0 3 + 2HC1 = 2LiCl + C 0 2 H20.

Normality of 5 0 - 0 0 ml acid used to dissolve
+
carbonate 1-00 Ν
Normality of acid after solution made up to
the mark in 2 5 0 ml flask (disregarding re-
action) 0-20 Ν
Hence acid present in 2 5 - 0 ml aliquot 25 0 ml of 0 - 2 0 Ν
50-0 ml of 0-1 O N
56 Τ Ï TR I METRIC AND GRAVIMETRIC ANALYSIS

By titration:
The excess 0-20 Ν hydrochloric acid is equivalent to 30-3 ml
0-10 Ν sodium hydroxide.
Therefore the volume of 0-10 Ν hydrochloric acid used in
reaction with carbonate
= (50-0 - 30-3) = 19-7 ml.
Thus 19-7 ml 0 1 0 Ν acid are equivalent to one-tenth weight of
carbonate taken.
Hence 1000 ml 1*0 Ν acid are equivalent to
/0-073 χ 1000\ , .
g carbonate
V 19-7
χ 0-1 /
= 37-05 g
Therefore equivalent weight of lithium carbonate is 37-1.
The correct value for the equivalent weight of lithium carbonate
when reacted with acids is 36-94.

I X . DETERMINATION OF CONCENTRATION OF SOME

CHEMICAL SALT SOLUTIONS USING ION-EXCHANGE RESINS
In these titrations, the solution being analysed is first placed in
contact with certain resinous substances capable of exchanging
ions present in the solution for ions from itself. The resin is
supplied in the form of small grains or beads and its molecular
structure is that of a cross-linked polymer network containing
some ionized or ionizable groups.
The type of resin known as a "cation-exchange" resin takes up
cations from a solution and exchanges them for hydrogen ions.
For example:
Res.H + NaCl ^ Res.Na + HCl
where Res. represents the resin, less the exchangeable cation. If
the resin and salt solution are merely put together in a vessel, an
equilibrium may be attained and so the exchange of hydrogen
ions for sodium ions will not be complete. If, however, the solution
 ACID-BASE TITRATIONS 57
is poured into the top of a column of resin, then the solution is
continually coming into contact with fresh portions of resin as it
passes downwards. Provided the column is sufficiently tall, the
solution not too concentrated and the size of resin particles and
the rate of flow are suitable, then the exchange will be complete
by the time the solution is collected at the bottom of the column.
The cation-exchange resin suitable for the above exchange is of a
type called "strongly acidic". There are also "strongly basic"
anion-exchange resins which remove anions from solutions,
replacing them with (for example) hydroxyl ions.
A fairly wide glass tube is partly filled with the resin, covered
with water, and the solution poured in at the top. (Full details of
procedure are given on p. 58). The solution is slowly run out at
the base of the column, collected in a flask and titrated. For
example, a dilute solution of sodium chloride, passed through a
column of a strongly acidic resin, will emerge as a solution of
hydrochloric acid. As the exchange is quantitative, the acid
produced is equivalent to the original solution. The acid may be
titrated in the usual manner. Afterwards, the resin may be
regenerated by placing it in a little hydrochloric acid to ensure
that it is in the acidic (hydrogen ion) form. The strongly basic
anion-exchanger is not usually kept in the hydroxide form
because the hydroxyl ion tends to take up carbon dioxide of the
air, being thus converted to the carbonate. It is usually in the
chloride form, from which it may readily be converted to the
hydroxide form by washing with dilute sodium hydroxide solution.
In both cases, the resins should be washed free of excess ions
by distilled water. When in use, resins should always be in contact
with water, that is, they should not be allowed to become dry.
These resins are, of course, sensitive to " s t r a y " ions and clean
glassware and a high grade of distilled water are required for good
results.
The total time taken for these ion-exchange titrations is longer
than for the other titrations described, but they do not often
require continuous attention. They do, however, allow the
58 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

volumetric estimation of a number of substances such as potassium

nitrate, for which no other simple titrimetric method exists. The
chemistry regarding the exchange of the ions may be found in
more advanced or specialized books. Many other such simple
determinations using, for example, silver nitrate or E D T A
solution, may be made using ion-exchange columns.t

( I ) DETERMINATION OF THE CONCENTRATION OF A SOLUTION

OF SODIUM SULPHATE
When a solution of sodium sulphate is allowed to run slowly
through a column of a strongly acidic cation-exchanger, the
sodium ions are exchanged for hydrogen ions. The acid solution
so produced is titrated with a standard alkali solution,

N a 2 S 0 4 + HRes. -> H 2 S 0 4 + NaRes.

Requirements
Cation-exchanger, strongly acidic type, e.g. Zeo-Karb 225
(sodium form), standard grade, mesh 14-52.
Burette to serve as column. A damaged burette, which has,
for example, the tap replaced by a piece of rubber tubing and a
screw clip, will do.
Glass-wool or \ in. diameter glass beads (obtainable from
laboratory suppliers).
Tap funnel.
2-3 Ν hydrochloric acid.
OT Ν (0-05 M) sodium sulphate solution.
Standardized 0-1 N sodium hydroxide solution.

Method
1. Take sufficient resin to half fill the burette, place in a small
beaker and well cover with dilute hydrochloric acid. Allow to
stand, with frequent stirrings, for 10 min. This is to ensure
f See, for example, Ion Exchange, by J. E. Salmon and D. K. Hale, and
Quantitative Inorganic Analysis, by Α. I. Vogel, 3rd ed., pp. 702-23.
 ACID—BASE TITRATIONS 59

FIG. 11. Apparatus for ion-exchange titration.

that the resin is in the "hydrogen" form. If the resin is already

in the column, from a previous experiment, then pass about
150 ml dilute hydrochloric acid through the resin.
2, Decant off the acid from the beaker (or allow to run through
60 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

the column), wash several times with distilled water until the
washings give no precipitate with silver nitrate solution.
3. Place \ in. wad of glass-wool in the burette, ram the wool
down to the bottom of the burette, with, for example, a long
glass rod. Preferably pack the bottom of the burette with
\ in. diameter glass beads as support for the resin.
4. Pour the mixture of resin and water into the burette, in portions,
with the aid of a funnel. Hold the funnel by hand to assist the
escape of the air from the burette. If necessary, t a p the burette
to dislodge air bubbles.
5. Clamp or support a tap-funnel over the burette. A very tall
clamp-stand is required, sometimes a nearby shelf can be used
to hold a clamp-stand.
6. Add about 15 ml water, using the tap-funnel. If the level of
the water is already well above the settled resin, this may not be
necessary. Next adjust the burette tap or screw clip so that
the water flows out at a rate of about 2-5 ml in 1 min. If
necessary, add more water so that the level of the water is
always above the resin. Place a conical flask beneath the burette.
7. Transfer a 25 ml aliquot of the sodium sulphate solution to
the tap-funnel, add 75 ml water and open the tap of the funnel.
Do not alter the rate of out-flow from the burette to the flask.
8. Wash the solution through with three separate portions of
about 40 ml each of distilled water, allowing the tap-funnel to
drain each time.
9. Titrate the acid collected in the flask with the standardized
0 1 Ν sodium hydroxide.

Calculation
From the known normality of the alkali solution, and the results
of the titrations, calculate the normality of the acid solution.
This normality is identical with that of the sodium sulphate
solution. Hence calculate the concentration of the sodium
sulphate solution.
Equivalent weight N a 2 S 0 4 = 71-02.
 ACID-BASE TITRATIONS 61
Regeneration
The resin now has sodium ions attached. To regain the hydrogen
form of the resin, allow dilute hydrochloric acid to flow down
the column or agitate the resin in a beaker of dilute hydrochloric
acid for 10 min. Then wash with water until the washings are
free of the acid (silver nitrate test).

( I I ) DETERMINATION OF THE CONCENTRATION OF A

SOLUTION OF POTASSIUM NITRATE
In this determination, a strongly basic anion-exchanger is
employed. When in contact with a potassium nitrate solution,
this type of resin takes u p the nitrate ions and liberates hydroxyl
ions into the solution. The alkaline solution is subsequently
titrated with an acid solution of known concentration.
K N 0 3 + Res.OH -> K O H + R e s . N 0 3 .

Requirements
Anion-exchanger, strongly basic type, e.g. De-Acidite FF
(chloride form) standard grade, mesh 14-52.
Column, etc., as in previous determination.
2-3 Ν sodium hydroxide solution.
0-05 Ν (0-05 Μ) potassium nitrate solution.
Standardized 0Ό5 Ν hydrochloric or sulphuric acid.

Method. Analogous to the previous determination. Convert

the resin to the "hydroxyl" form, by passing 150 ml dilute sodium
hydroxide solution through the resin in the column. Titrate the
potassium hydroxide collected in the flask with standardized
0-05 Ν acid.

Calculation. Analogous to that of the previous experiment.

Equivalent weight KNO3 = 101-11.

62 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Suggestions for variations on acid-base titration exercises

The tables on p p . 174-5 may be useful in the preparation of
the solutions mentioned.

1. Given borax crystals and an approximately decinormal

solution of a strong acid, determine the equivalent weight of
(1) the alkali carbonate dissolved in solution " X " which contains
(a given number) g per litre carbonate, and (ii) the equivalent
weight of the given metallic oxide " Y " .
" X " could be potassium bicarbonate or sodium carbonate
and " Y " could be magnesium oxide. F o r the latter estimation,
follow the instructions for finding the equivalent weight of a
metal, take about 0-5 g of the oxide.

2. Estimate the purity of (1) the given sample of chalk and

(2) the sample of sodium hydrogen sulphate by means of the
provided anhydrous sodium carbonate. Approximately 0-1 M
hydrochloric acid and approximately 0*1 M potassium hydroxide
solutions are also available.

3. Use the given potassium bicarbonate to determine the

normality of the given hydrochloric acid solution. Then use this
acid to determine the value of η of the sodium carbonate hydrate
crystals, N a 2 C 0 3 H H 2 0 , used to prepare solution " X " which
contains (a stated value) grams per litre of the hydrate.
η may, of course, be (approximately) either 1 or 10. Sodium
sesquicarbonate, N a 2 C 0 3 N a H C 0 3 - 2 H 2 0 , may be given as a
variation of the above exercise. The calculation is similar to that
shown on p. 69.

4. Given succinic acid crystals determine the normality of the

given sodium hydroxide solution and hence find the number of
molecules of water of crystallization in the given dibasic organic
acid crystals. The anhydrous acid has a molecular weight of 90Ό.
The acid crystals are oxalic acid dihydrate.
 ACID-BASE TITRATIONS 63
5. Determine the normality of the given barium hydroxide
solution and hence find the normality and concentration in
grams per litre of the given acetic acid solution. Concentrated
hydrochloric acid, distillation apparatus and a table of the
composition of constant boiling hydrochloric acid solutions are
provided.
Instead of the hydrochloric acid, potassium biphthalate crystals
or potassium tetroxalate crystals or any of the organic acids,
mentioned on p . 52, could be given.

6. The given solution contains both ammonium sulphate and

ammonium chloride. Determine the concentration of the am-
monium chloride by titration with silver nitrate solution (see
p. 68) and then determine the total ammonium content by
either of the methods on p . 43. Hence, by subtraction, determine
the concentration of ammonium sulphate in the solution.

7. Determine the concentration of hydrochloric acid in the

given solution which contains both nitric and hydrochloric acids.
A solution of silver nitrate, of given concentration, is provided.
Then determine the total hydrogen ion concentration in gram-ions
per litre, using the given borax crystals. Thus calculate the
concentration of the nitric acid, by subtraction.
A solution containing hydrochloric acid and an alkali chloride
may be estimated in a similar way, given a standard silver nitrate
solution and a standard alkali solution.

8. Solutions of aluminium chloride are hydrolysed to such a

large extent that they may be titrated with sodium hydroxide as
if they were solutions of free hydrochloric acid. Precipitation of
aluminium hydroxide may occur during the titration but never-
theless a satisfactory end-point is obtained.

A1C1 3 + 3 H 2 0 ^ A l ( O H ) 3 + 3HC1

or [ A 1 ( H 20 ) 6] 3 + + H 2 0 - [ A l ( H 20 ) 5( O H ) ] 2 + + H 3 0 + .

D
64 TITRIMETRIC AND GRAVIMETRIC ANALYSIS

Phenolphthalein is used as indicator.

Determine the concentration of the solution of aluminium
chloride by two different methods. Standard solutions of sodium
hydroxide and silver nitrate are given (see p. 7 2 ) .

9. Given ammonium ferrous sulphate crystals, determine the

normality of the given potassium permanganate solution and
hence determine the normality of the given oxalic acid solution
(see p. 85). Check the accuracy of working by determining the
normality of the oxalic acid solution using a standardized sodium
hydroxide solution.

10. Determine the equivalent weight of " X " when acting as a

reducing agent and when acting as an acid. Solutions of given
concentration of potassium permanganate and sodium hydroxide
are provided.
" X " is oxalic acid crystals or a solution of oxalic acid of given
concentration. Potassium tetroxalate, ( C O O H ) 2 C O O H C O O K ,
may also be given ; it has the advantage of serving as a reminder
that the equivalent weight may vary with the reaction. Brief
instructions, e.g. regarding weight to be taken, should be given.
11. By means of the given potassium iodate crystals, determine
the normality of the hydrochloric acid solution. 5 % potassium
iodide solution, 0-1 Ν sodium thiosulphate solution and methyl
red indicator are provided.
The reaction between iodate, iodide and hydrogen ions is:

I 0 3 - + 5 1 " + 6 H + -> 3 I 2 + 3 H 2 0

(see p. 111). If the reaction is carried out in the presence of excess

iodide ions and excess thiosulphate ions, then the iodine that is
liberated is immediately removed. Place 25 ml aliquots of deci-
normal potassium iodate solution, 1 g potassium iodide, about
40 ml decinormal thiosulphate solution and methyl red indicator
in the conical flasks and titrate with the acid. The first drop of
excess acid may be detected by the change in colour of the methyl
red indicator.